Method for producing substrate with patterned film

ABSTRACT

The production method of a substrate with a patterned film according to the present disclosure includes: a cleaning step of performing UV/ozone cleaning or oxygen plasma cleaning on a substrate with a patterned film including a substrate and a patterned film on the substrate, to obtain a first substrate with a patterned film; and a heating step of heating the first substrate with a patterned film to obtain a second substrate with a patterned film, wherein the patterned film of the first substrate with a patterned film has a contact angle decreased in the cleaning step, and the patterned film of the second substrate with a patterned film has a contact angle recovered in the heating step.

TECHNICAL FIELD

The present disclosure relates to a method for producing a substratewith a patterned film. The production method of a substrate with apatterned film of the present disclosure can be used, for example, forproduction of a display element by an ink-jet method. Examples of thedisplay element include an organic electroluminescence display(hereafter, referred to as an organic EL display), a micro lightemitting diode display (hereafter, referred to as a micro-LED display),and a quantum dot display.

BACKGROUND ART

An ink-jet method is known to be employed for production of displayelements such as an organic EL display, a micro-LED display, and aquantum dot display.

Examples of a production method of these display elements by an ink-jetmethod include a method of forming a pattern by unevenness of a film ona substrate and dropping ink through a nozzle onto the recesses of thepattern, followed by solidifying of the ink, and a method of forming apatterned film including a lyophilic part to be wetted with ink and alyophobic part that repels ink on a substrate in advance and droppingink on the patterned film to adhere the ink to the lyophilic part.

In the method of dropping ink through a nozzle onto depressions(recesses) of the patterned film having unevenness and solidifying theink, such a patterned film is produced by photolithography orimprinting. In the photolithography, a resist film formed on a substrateis exposed in a pattern, whereby a pattern including an exposed part andan unexposed part is formed. Either one part is dissolved in adeveloping solution to provide the resist film with unevenness. In theimprinting, a patterned film with unevenness is formed on a substrate bya printing technique. In such a patterned film with unevenness, thesubstrate surface is preferably exposed in the recesses and the exposedsubstrate surface is preferably lyophilic.

In an ink-jet method, a protrusion of a patterned film with unevennessis called a bank. The bank serves as a barrier for preventing mixing ofink upon dropping of ink onto the recesses of the patterned film byink-jetting.

For example, Patent Literature 1 discloses a composition for an organicEL element used as ink in the production of an organic EL display by anink-jet method. According to Patent Literature 1, a bank is formed on asubstrate in advance, and ink (a composition for an organic EL element)to be formed into a light emitting layer is dropped, whereby a displayelement for an organic EL display is produced.

Patent Literature 2 discloses a method for producing a color filter fora liquid crystal, including forming a photosensitive compound layercontaining a hydrophobic and lipophobic compound having a surfacetension or a critical surface tension of 2.5×10⁻² [N/m] or less byphotolithography on a light shielding part formed on alight-transmitting substrate, and arranging a colorant on alight-transmitting part of the substrate by ink ejection using anink-jet recorder. According to Patent Literature 2, the presence of afluoropolymer or a fluorochemical surfactant in the photosensitivecompound layer forming a bank enhances the lyophobicity of the bank andsuch a bank prevents intrusion of ink over the bank into the adjacentrecess upon dropping of the ink onto the recesses of the patterned filmby ink-jetting.

Patent Literature 3 discloses a lyophobic resist composition forobtaining a pattern including a lyophobic region and a lyophilic regionby photolithography. According to Patent Literature 3, the use of thelyophobic resist composition enables formation of a lyophobic/lyophilicpattern having a clear ink-wetting contrast by an ink-jet method. Thesubstrate surface serving as a recess is made lyophilic and the banksurface is made lyophobic for the purpose of preventing intrusion of inkover the bank into the adjacent recess upon dropping of the ink onto therecesses of the patterned film by an ink-jet method.

Patent Literature 4 discloses a patterning substrate used in an ink-jetmethod. The patterning substrate contains a thin film including a bankhaving a predetermined height and a region to be coated which ispartitioned by the bank. According to Patent Literature 4, the region tobe coated which is a recess is lyophilic and the bank which is aprotrusion is lyophobic.

Patent Literature 5 discloses a positive photosensitive resincomposition that is capable of forming an image and provides a curedfilm having high hydrophobicity and lipophobicity on the surface.According to Patent Literature 5, the positive photosensitive resincomposition is suitably used for an interlayer insulating film in sdisplay device such as a liquid crystal display or an EL display, and alight shielding material and partition material each compatible with anink-jet method.

According to Patent Literatures 4 and 5, a recess of a patterned film islyophobic due to failures such as organic contamination of the substratesurface as the recess of the patterned film in the case of forming thepatterned film on a substrate by photolithography and film residues onthe recess of the patterned film in the case of forming the patternedfilm by imprinting. Therefore, the substrate with a patterned filmprovided using a hydrophilic ink is subjected to hydrophilization, sothat the recess of the patterned film is made hydrophilic. Thehydrophilization allows the recess of the patterned film not to repelink in ink-jetting. Accordingly, dropping of ink onto the substrate witha patterned film is facilitated.

According to Patent Literature 4, contact between a substrate with apatterned film and oxygen plasma gas and fluorine plasma gas allows thesubstrate surface that is a recess of the patterned film to havehydrophilicity and the bank that is a protrusion of the patterned filmto have hydrophobicity.

According to Patent Literature 5, the positive photosensitive resincomposition of the disclosure can provide a substrate with a patternedfilm in which the surface of the patterned film serving as a bankmaintains high lyophobicity even after UV/ozone cleaning during thehydrophilization.

CITATION LIST

Patent Literature

-   Patent Literature 1: JP H11-54270 A-   Patent Literature 2: JP H10-197715 A-   Patent Literature 3: JP 2012-220860 A-   Patent Literature 4: JP 2000-353594 A-   Patent Literature 5: WO 2017/126610

SUMMARY OF INVENTION Technical Problem

As described in Patent Literatures 4 and 5, UV/ozone cleaning or oxygenplasma cleaning is performed on a substrate with a patterned film forthe purpose of increasing the lyophilicity of the substrate surface thatis a recess of the patterned film. Unfortunately, the cleaning lowersthe lyophobicity of the bank. In such a case, upon dropping of ink ontothe recess of the patterned film by an ink-jet method, the ink may climbover the bank or the bank may be dissolved in the ink.

The present disclosure provides a production method of a substrate witha patterned film for solving the above problem.

Solution to Problem

The present inventors made intensive studies to solve the above problem,and found out the following fact. UV/ozone cleaning or oxygen plasmacleaning performed on a substrate with a patterned film containing aspecific fluorine-containing copolymer lowers the lyophobicity of thepatterned film once. However, heating treatment performed thereafterprovides the lyophobicity (recovers the lyophobicity).

A patterned film containing a specific fluorine-containing copolymerafter UV/ozone cleaning or oxygen plasma cleaning showed lowerlyophobicity against water and anisole used as an ink solvent in anink-jet method. Heating of the patterned film however recovered thelyophobicity against both water and anisole (see Tables 2 and 4 ofEXAMPLES herein). Similarly, a patterned film containing a specificfluorine-containing copolymer after UV/ozone cleaning or oxygen plasmacleaning also showed lower lyophobicity against propylene glycolmonomethyl ether acetate (PGMEA) and xylene. Heating of the patternedfilm however recovered the lyophobicity against both PGMEA and xylene(see Tables 6 and 8 of EXAMPLES herein). As described above, the presentinventors found out that heating of a patterned film containing aspecific fluorine-containing copolymer after UV cleaning unexpectedlyremarkably recovers the lyophobicity.

The surface of a patterned film subjected to UV/ozone cleaning or oxygenplasma cleaning is oxidized to be lyophilic. However, owing to the useof a special fluorine-containing copolymer capable of suppressingcleavage of the polymer main chain, presumably, alkyl fluoride partshaving a small surface free energy move to the film surface along withthe molecular motion caused by heating, whereby the lyophobicity isrecovered.

UV/ozone cleaning herein refers to a method of removing organiccontaminants. In the method, a substrate with a patterned film isirradiated with UV rays for decomposition of binding of organiccontaminants adhering to the patterned film and a recess of thesubstrate with a patterned film, and at the same time, active oxygenseparated from ozone generated by UV irradiation chemically binds to theorganic contaminants to decompose the organic contaminants to volatilematters such as carbon dioxide and water. Thus, organic contaminants areremoved. The UV irradiation device typically used is a low-pressuremercury lamp.

Oxygen plasma cleaning herein refers to a method of removing organiccontaminants. In the method, a high voltage is applied to gas containingoxygen molecules to dissociate oxygen molecules, thereby generatingactive oxygen. The active oxygen decomposes organic contaminantsadhering to the surface of the substrate with a patterned film tovolatile matters such as carbon dioxide and water. Thus, organiccontaminants are removed.

The following inventions 1 to 22 are disclosed.

[Invention 1]

A method for producing a substrate with a patterned film, the methodincluding:

a cleaning step of performing UV/ozone cleaning or oxygen plasmacleaning on a substrate with a patterned film comprising a substrate anda patterned film on the substrate, to obtain a first substrate with apatterned film; and

a heating step of heating the first substrate with a patterned film toobtain a second substrate with a patterned film,

wherein the patterned film of the first substrate with a patterned filmhas a contact angle decreased in the cleaning step, and

the patterned film of the second substrate with a patterned film has acontact angle recovered in the heating step.

[Invention 2]

The production method according to Invention 1,

wherein an angle obtained by subtracting a contact angle with anisole ofthe patterned film of the first substrate with a patterned film from acontact angle with anisole of the patterned film of the second substratewith a patterned film is represented by D_(A1), and

D_(A1) is 10° or larger.

[Invention 3]

The production method according to Invention 2, wherein an angleobtained by subtracting the contact angle with anisole of the patternedfilm of the first substrate with a patterned film from a contact anglewith anisole of the patterned film before the cleaning step isrepresented by D_(A0), and

a value of D_(A1)/D_(A0) is 0.30 or larger.

[Invention 4]

The production method according to any one of Inventions 1 to 3,

wherein an angle obtained by subtracting a contact angle with water ofthe patterned film of the first substrate with a patterned film from acontact angle with water of the patterned film of the second substratewith a patterned film is represented by D_(W1),

D_(W1) is 10° or larger,

an angle obtained by subtracting the contact angle with water of thepatterned film of the first substrate with a patterned film from acontact angle with water of the patterned film before the cleaning stepis represented by D_(W0), and

a value of D_(W1)/D_(W0) is 0.50 or larger.

[Invention 5]

The production method according to any one of Inventions 1 to 4,

wherein an angle obtained by subtracting a contact angle with propyleneglycol monomethyl ether acetate of the patterned film of the firstsubstrate with a patterned film from a contact angle with propyleneglycol monomethyl ether acetate of the patterned film of the secondsubstrate with a patterned film is represented by D_(P1), and

D_(P1) is 10° or larger.

[Invention 6]

The production method according to Invention 5,

wherein an angle obtained by subtracting the contact angle withpropylene glycol monomethyl ether acetate of the patterned film of thefirst substrate with a patterned film from a contact angle withpropylene glycol monomethyl ether acetate of the patterned film beforethe cleaning step is represented by D_(P0), and

a value of D_(P1)/D_(P0) is 0.30 or larger.

[Invention 7]

The production method according to any one of Inventions 1 to 6,

wherein an angle obtained by subtracting a contact angle with xylene ofthe patterned film of the first substrate with a patterned film from acontact angle with xylene of the patterned film of the second substratewith a patterned film is represented by D_(X1), and

D_(X1) is 15° or larger.

[Invention 8]

The production method according to Invention 7,

wherein an angle obtained by subtracting the contact angle with xyleneof the patterned film of the first substrate with a patterned film froma contact angle with xylene of the patterned film before the cleaningstep is represented by D_(X0), and

a value of D_(X1)/D_(X0) is 0.80 or larger.

[Invention 9]

The production method according to any one of Inventions 1 to 8,

wherein the patterned film of the first substrate with a patterned filmhas a contact angle with water of 50° or larger and a contact angle withanisole of 30° or larger, and

the patterned film of the second substrate with a patterned film has acontact angle with water of 93° or larger and a contact angle withanisole of 50° or larger.

[Invention 10]

The production method according to any one of Inventions 1 to 9,

wherein the patterned film of the first substrate with a patterned filmhas a contact angle with propylene glycol monomethyl ether acetate of19° or larger and a contact angle with xylene of 20° or larger, and

the patterned film of the second substrate with a patterned film has acontact angle with propylene glycol monomethyl ether acetate of 40° orlarger and a contact angle with xylene of 45° or larger.

[Invention 11]

The production method according to any one of Inventions 1 to 10,

wherein the patterned film contains a fluorine-containing copolymerhaving a repeating unit represented by the following formula (A):

wherein R¹ is a hydrogen atom, a fluorine atom, or a C1-C20 alkyl groupin which hydrogen atoms bonded to a carbon atom are optionally partly orentirely replaced by fluorine atoms; Q is a C1-C20 fluoroalkyl groupoptionally containing a hydrogen atom, an oxygen atom, or a nitrogenatom; X is a single bond or a divalent group; and O is an oxygen atom.

[Invention 12]

The production method according to Invention 11,

wherein the fluorine-containing copolymer is any one of the followingfluorine-containing copolymers (1) to (3):

the fluorine-containing copolymer (1) containing both the repeating unitrepresented by the following formula (A) and a repeating unitrepresented by the following formula (B):

wherein R¹ and R² are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X and Y are each independently a singlebond or a divalent group, O is an oxygen atom; and H is a hydrogen atom;

the fluorine-containing copolymer (2) containing both the repeating unitrepresented by the following formula (A) and a repeating unitrepresented by the following formula (C):

wherein R¹ and R³ are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X is a single bond or a divalent group;Z is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynylgroup, a C6-C20 phenyl group, a C1-C20 alkoxy group, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and a hydrogen atom in any of theforegoing groups is optionally replaced by a fluorine atom, an oxygenatom, or a nitrogen atom; and O is an oxygen atom;

The fluorine-containing copolymer (3) containing all of the repeatingunit represented by the following formula (A), the repeating unitrepresented by the following formula (B), and the repeating unitrepresented by the following formula (C):

wherein R¹, R², R³ are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X and Y are each independently a singlebond or a divalent group; Z is a C1-C20 alkyl group, a C2-C20 alkenylgroup, a C2-C20 alkynyl group, a C6-C20 phenyl group, a C1-C20 alkoxygroup, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and ahydrogen atom in any of the foregoing groups is optionally replaced by afluorine atom, an oxygen atom, or a nitrogen atom; 0 is an oxygen atom;and H is a hydrogen atom.

[Invention 13]

The production method according to any one of Inventions 1 to 12,

wherein the first substrate with a patterned film is heated at atemperature of 50° C. or higher but 350° C. or lower for 10 seconds orlonger in the heating step.

[Invention 14]

The production method according to any one of Inventions 1 to 13,

wherein the second substrate with a patterned film is a substrate forforming a display element by an ink-jet method.

[Invention 15]

The production method according to any one of Inventions 11 to 14,

wherein Q is a C3-C10 fluoroalkyl group and X is a carbonyl group in therepeating unit represented by the formula (A).

[Invention 16]

The production method according to Invention 15,

wherein Q is a perfluorohexyl ethyl group and X is a carbonyl group inthe repeating unit represented by the formula (A).

[Invention 17]

The production method according to Invention 15,

wherein Q is a hexafluoroisopropyl group and X is a carbonyl group inthe repeating unit represented by the formula (A).

[Invention 18]

The production method according to any one of Inventions 11 to 14,

wherein the repeating unit represented by the formula (A) is a repeatingunit represented by the following formula (4):

wherein R⁴ and R⁵ are each independently a hydrogen atom, a fluorineatom, or a C1-C3 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; 0 isan oxygen atom; H is a hydrogen atom; and F is a fluorine atom.

[Invention 19]

The production method according to any one of Inventions 12 to 14,

wherein Q is a hexafluoroisopropyl group and X is a carbonyl group inthe repeating unit represented by the formula (A), and Y is ap-phenylene group or a carboxy ethylene group in the repeating unitrepresented by the formula (B).

[Invention 20]

The production method according to any one of Inventions 12 to 14,

wherein Q is a hexafluoroisopropyl group and X is a carbonyl group inthe repeating unit represented by the formula (A); Y is a p-phenylenegroup or a carboxy ethylene group in the repeating unit represented bythe formula (B); and Z is an alkoxy group, a carboxyl group, an acetoxygroup, or a bis(trifluoromethyl)vinyl group in the repeating unitrepresented by the formula (C).

[Invention 21]

The production method according to any one of Inventions 12 to 14,

wherein Z is a bis(trifluoromethyl)vinyl group in the repeating unitrepresented by the formula (C).

[Invention 22]

The production method according to any one of Inventions 12 to 14,

wherein Q is a C3-C10 fluoroalkyl group and X is a carbonyl group in therepeating unit represented by the formula (A); Y is a p-phenylene group,a p-phenylene carbonyl group, or a p-phenylene hexafluoroisopropylenegroup in the repeating unit represented by the formula (B); and Z is abis(trifluoromethyl)vinyl group in the repeating unit represented by theformula (C).

Advantageous Effects of Invention

According to the production method of a substrate with a patterned filmof the present disclosure, a patterned film can have sufficientlyophobicity while maintaining the lyophilicity of a substrate surfacethat is a recess of the patterned film. Even after UV/ozone cleaning oroxygen plasma cleaning of the surface of the patterned film, thelyophobicity of the patterned film can be recovered by heating of thepatterned film.

DESCRIPTION OF EMBODIMENTS

The present invention is not limited to the following embodiments, andmodifications or changes may be suitably made based on the conventionalknowledge of a person skilled in the art without departing from the gistof the present invention. It should be understood that such a modifiedor changed invention is also encompassed by the present invention.

1. Heating Treatment after UV/Ozone Cleaning or Oxygen Plasma Cleaning

The production method of a substrate with a patterned film of thepresent disclosure includes a cleaning step of performing UV/ozonecleaning or oxygen plasma cleaning on a substrate with a patterned filmto obtain a first substrate with a patterned film, and a heating step ofheating the first substrate with a patterned film to obtain a secondsubstrate with a patterned film.

The heating temperature in the heating step is preferably 50° C. orhigher but 350° C. or lower, more preferably 100° C. or higher but 300°C. or lower, still more preferably 150° C. or higher but 250° C. orlower. The heating temperature of lower than 50° C. is not likely toprovide the effect of recovering the lyophobicity of the substrate witha patterned film, which has been lowered by UV/ozone cleaning or oxygenplasma cleaning, to the same or substantially the same level as thatbefore UV/ozone cleaning or oxygen plasma cleaning.

The upper limit of the heating time is not limited, and the heating timeis preferably adjusted in accordance with the heat resistance of thephotoresist used for pattern formation of the substrate with a patternedfilm. Though not limited, the upper limit of the heating time ispractically one hour or shorter. The lower limit of the heating time ispreferably 10 seconds or longer, more preferably 30 seconds or longer.The heating time of shorter than 10 seconds is not likely to provide theeffect of recovering the lyophobicity of the substrate with a patternedfilm, which has been lowered by UV/ozone cleaning or oxygen plasmacleaning, to the same or substantially the same level as that beforeUV/ozone cleaning or oxygen plasma cleaning.

The heating means used may be a commonly available heating device.Examples thereof include a hot plate and an oven.

The heating may be performed in an environment, such as in nitrogen gasor under reduced pressure. Preferably, the heating is performed in theatmosphere (air) at normal pressure (101.325 kPa) as a commerciallyavailable heating device is usable.

According to the production method of a substrate with a patterned filmof the present disclosure, the patterned film of the first substratewith a patterned film has a contact angle decreased in the cleaningstep. However, the patterned film of the second substrate with apatterned film has a contact angle recovered in the heating step.

An angle obtained by subtracting a contact angle with anisole of thepatterned film of the first substrate with a patterned film from acontact angle with anisole of the patterned film of the second substratewith a patterned film is represented by D_(A1). D_(A1) is preferably 10°or larger. D_(A1) is also preferably 70° or smaller, more preferably 65°or smaller, particularly preferably 50° or smaller.

The value of D_(A1) is obtained by the formula: θ_(A2)−θ_(A1), whereθ_(A1) represents the contact angle with anisole of the patterned filmof the first substrate with a patterned film and θ_(A2) represents thecontact angle with anisole of the patterned film of the second substratewith a patterned film.

An angle obtained by subtracting the contact angle with anisole of thepatterned film of the first substrate with a patterned film from acontact angle with anisole of the patterned film before the cleaningstep is represented by D_(A0). A value of D_(A1)/D_(A0) is preferably0.30 or larger. The value of D_(A1)/D_(A0) is also preferably 1.20 orsmaller, more preferably 1.15 or smaller, particularly preferably 1.10or smaller.

The value of D_(A0) is obtained by the formula: θ_(A0)−θ_(A1), whereθ_(A0) represents the contact angle with anisole of the patterned filmbefore the cleaning step.

The contact angle θ_(A1) with anisole of the patterned film of the firstsubstrate with a patterned film is preferably 15° or larger, morepreferably 30° or larger. The contact angle θ_(A1) with anisole of thepatterned film of the first substrate with a patterned film ispreferably 65° or smaller, more preferably 63° or smaller.

The contact angle θ_(A2) with anisole of the patterned film of thesecond substrate with a patterned film is preferably 50° or larger. Thecontact angle θ_(A2) with anisole of the patterned film of the secondsubstrate with a patterned film is preferably 85° or smaller, morepreferably 83° or smaller.

The contact angle θ_(A0) with anisole of the patterned film before thecleaning step is preferably 50° or larger. The contact angle θ_(A0) withanisole of the patterned film before the cleaning step is alsopreferably 85° or smaller, more preferably 83° or smaller.

An angle obtained by subtracting a contact angle with water of thepatterned film of the first substrate with a patterned film from acontact angle with water of the patterned film of the second substratewith a patterned film is represented by D_(W1). D_(W1) is preferably 10°or larger. D_(W1) is also preferably 90° or smaller, more preferably 65°or smaller.

The value of D_(W1) is obtained by the formula: θ_(W2)−θ_(W1), whereθ_(W1) represents the contact angle with water of the patterned film ofthe first substrate with a patterned film and θ_(W2) represents thecontact angle with water of the patterned film of the second substratewith a patterned film.

An angle obtained by subtracting the contact angle with water of thepatterned film of the first substrate with a patterned film from acontact angle with water of the patterned film before the cleaning stepis represented by D_(W0). A value of D_(W1)/D_(W0) is preferably 0.50 orlarger. The value of D_(W1)/D_(W0) is also preferably 1.20 or smaller,more preferably 1.15 or smaller, particularly preferably 1.10 orsmaller.

The value of D_(W0) is obtained by the formula: θ_(W0)−θ_(W1), whereθ_(N0) represents the contact angle with water of the patterned filmbefore the cleaning step.

The contact angle θ_(W1) with water of the patterned film of the firstsubstrate with a patterned film is preferably 30° or larger, morepreferably 50° or larger. The contact angle θ_(W1) with water of thepatterned film of the first substrate with a patterned film is alsopreferably 100° or smaller, more preferably 98° or smaller.

The contact angle θ_(W2) with water of the patterned film of the secondsubstrate with a patterned film is preferably 93° or larger. The contactangle θ_(W2) with water of the patterned film of the second substratewith a patterned film is also preferably 120° or smaller, morepreferably 115° or smaller.

The contact angle θ_(W0) with water of the patterned film before thecleaning step is preferably 95° or larger. The contact angle θ_(W0) withwater of the patterned film before the cleaning step is also preferably120° or smaller, more preferably 115° or smaller.

In particular, preferably, the patterned film of the first substratewith a patterned film has a contact angle θ_(W1) with water of 50° orlarger and a contact angle θ_(A1) with anisole of 30° or larger, and thepatterned film of the second substrate with a patterned film has acontact angle θ_(W2) with water of 93° or larger and a contact angleθ_(A2) with anisole of 50° or larger.

An angle obtained by subtracting a contact angle with propylene glycolmonomethyl ether acetate (PGMEA) of the patterned film of the firstsubstrate with a patterned film from a contact angle with propyleneglycol monomethyl ether acetate (PGMEA) of the patterned film of thesecond substrate with a patterned film is represented by D_(P1). D_(P1)is preferably 10° or larger. Da is also preferably 55° or smaller, morepreferably 40° or smaller.

The value of D_(P1) is obtained by the formula: θ_(P2)−θ_(P1), whereθ_(P1) represents the contact angle with PGMEA of the patterned film ofthe first substrate with a patterned film and θ_(P2) represents thecontact angle with PGMEA of the patterned film of the second substratewith a patterned film.

An angle obtained by subtracting the contact angle with propylene glycolmonomethyl ether acetate of the patterned film of the first substratewith a patterned film from a contact angle with propylene glycolmonomethyl ether acetate of the patterned film before the cleaning stepis represented by D_(P0). A value of D_(P1)/D_(P0) is preferably 0.30 orlarger. The value of D_(P1)/D_(P0) is also preferably 1.20 or smaller,more preferably 1.18 or smaller, particularly preferably 1.15 orsmaller.

The value of D_(P0) is obtained by the formula: θ_(P0)−θ_(P1), whereθ_(P0) represents the contact angle with PGMEA of the patterned filmbefore the cleaning step.

The contact angle θ_(P1) with PGMEA of the patterned film of the firstsubstrate with a patterned film is preferably 15° or larger, morepreferably 19° or larger. The contact angle θ_(P1) with PGMEA of thepatterned film of the first substrate with a patterned film is alsopreferably 45° or smaller, more preferably 40° or smaller.

The contact angle θ_(P2) with PGMEA of the patterned film of the secondsubstrate with a patterned film is preferably 40° or larger. The contactangle θ_(P2) with PGMEA of the patterned film of the second substratewith a patterned film is also preferably 70° or smaller, more preferably68° or smaller.

The contact angle θ_(P0) with PGMEA of the patterned film before thecleaning step is preferably 40° or larger. The contact angle θ_(P0) withPGMEA of the patterned film before the cleaning step is also preferably70° or smaller, more preferably 68° or smaller.

An angle obtained by subtracting a contact angle with xylene of thepatterned film of the first substrate with a patterned film from acontact angle with xylene of the patterned film of the second substratewith a patterned film is represented by D_(X1). D_(X1) is preferably 15°or larger. D_(X1) is also preferably 60° or smaller, more preferably 50°or smaller.

The value of D_(X1) is obtained by the formula: θ_(X2)−θ_(X1), whereθ_(X1) represents the contact angle with xylene of the patterned film ofthe first substrate with a patterned film and θ_(X2) represents thecontact angle with xylene of the patterned film of the second substratewith a patterned film.

An angle obtained by subtracting the contact angle with xylene of thepatterned film of the first substrate with a patterned film from acontact angle with xylene of the patterned film before the cleaning stepis represented by D_(X0). A value of D_(X1)/D_(X0) is preferably 0.80 orlarger. The value of D_(X1)/D_(X0) is also preferably 1.20 or smaller,more preferably 1.18 or smaller, particularly preferably 1.15 orsmaller.

The value of D_(X0) is obtained by the formula: θ_(X0)−θ_(X1), whereθ_(X0) represents the contact angle with xylene of the patterned filmbefore the cleaning step.

The contact angle θ_(X1) with xylene of the patterned film of the firstsubstrate with a patterned film is preferably 15° or larger, morepreferably 20° or larger. The contact angle θ_(X1) with xylene of thepatterned film of the first substrate with a patterned film is alsopreferably 50° or smaller, more preferably 45° or smaller.

The contact angle θ_(X2) with xylene of the patterned film of the secondsubstrate with a patterned film is preferably 45° or larger. The contactangle θ_(X2) with xylene of the patterned film of the second substratewith a patterned film is also preferably 75° or smaller, more preferably73° or smaller.

The contact angle θ_(X0) with xylene of the patterned film before thecleaning step is preferably 45° or larger. The contact angle θ_(X0) withxylene of the patterned film before the cleaning step is also preferably75° or smaller, more preferably 73° or smaller.

In particular, preferably, the patterned film of the first substratewith a patterned film has a contact angle θ_(P1) with PGMEA of 19° orlarger and a contact angle θ_(X1) with xylene of 20° or larger, and thepatterned film of the second substrate with a patterned film has acontact angle θ_(P2) with PGMEA of 40° or larger and a contact angleθ_(X2) with xylene of 45° or larger.

According to the production method of a substrate with a patterned filmof the present disclosure, a substrate with a patterned film including asubstrate and a patterned film on the substrate is heated after UV/ozonecleaning or oxygen plasma cleaning, which reduces the problem that, upondropping of ink onto a recess of the patterned film of the substratewith a patterned film by an ink-jet method, the ink climbs over a bankor the bank is dissolved in the ink.

2. Fluorine-Containing Copolymer

In the production method of a substrate with a patterned film of thepresent disclosure, the substrate with a patterned film includes asubstrate and a patterned film on the substrate. The patterned filmpreferably contains a fluorine-containing copolymer containing arepeating unit represented by the following formula (A).

(In the formula, R¹ is preferably a hydrogen atom, a fluorine atom, or aC1-C20 alkyl group in which hydrogen atoms bonded to a carbon atom areoptionally partly or entirely replaced by fluorine atoms; Q is a C1-C20fluoroalkyl group optionally containing a hydrogen atom, an oxygen atom,or a nitrogen atom; X is a single bond or a divalent group; and O is anoxygen atom.)

In the production method of a substrate with a patterned film of thepresent invention, the fluorine-containing copolymer containing arepeating unit represented by the formula (A) is preferably any one ofthe following fluorine-containing copolymers (1) to (3) as a resistcontaining such a fluorine-containing copolymer repels ink when used forpattern formation.

[Fluorine-Containing Copolymer (1)]

The fluorine-containing copolymer (1) contains both a repeating unitrepresented by the following formula (A) (hereafter, also referred to asa repeating unit (A)) and a repeating unit represented by the followingformula (B) (hereafter, also referred to as a repeating unit (B)).

(In the formulas, R¹ and R² are each independently a hydrogen atom, afluorine atom, or a C1-C20 alkyl group in which hydrogen atoms bonded toa carbon atom are optionally partly or entirely replaced by fluorineatoms; Q is a C1-C20 fluoroalkyl group optionally containing a hydrogenatom, an oxygen atom, or a nitrogen atom; X and Y are each independentlya single bond or a divalent group; 0 is an oxygen atom; and H is ahydrogen atom.)

In the fluorine-containing copolymer (1), preferably, Q is ahexafluoroisopropyl group (—CH(CF₃)₂) and X is a carbonyl group(—C(═O)—) in the repeating unit represented by the formula (A), and Y isa carboxy ethylene group (—C(═O)—O—CH₂CH₂—) in the repeating unitrepresented by the formula (B).

Preferred combinations of the repeating unit (A) and the repeating unit(B) are listed below.

<Repeating Unit Content>

The repeating unit (A) content in terms of mol % relative to the sum ofthe repeating units (A) and (B) in the fluorine-containing copolymer (1)is preferably 5% or higher but 90% or lower, more preferably 10% orhigher but 80% or lower.

The fluorine-containing copolymer (1) may contain, if necessary, arepeating unit other than the repeating units (A) and (B) for thepurpose of improving the solubility in an organic solvent oradhesiveness to a substrate or hardness when formed into a film. Therepeating unit content other than the repeating units (A) and (B) interms of mol % relative to the sum of the repeating units (A) and (B) ispreferably 50% or lower, more preferably 30% or lower. The repeatingunit content other than the repeating units (A) and (B) of higher than50% tends to fail to achieve the lyophobicity.

[Fluorine-Containing Copolymer (2)]

The fluorine-containing copolymer (2) contains both a repeating unitrepresented by the following formula (A) and a repeating unitrepresented by the following formula (C) (hereafter, also referred to asa repeating unit (C)).

(In the formulas, R¹ and R³ are each independently a hydrogen atom, afluorine atom, or a C1-C20 alkyl group in which hydrogen atoms bonded toa carbon atom are optionally partly or entirely replaced by fluorineatoms; Q is a C1-C20 fluoroalkyl group optionally containing a hydrogenatom, an oxygen atom, or a nitrogen atom; X is a single bond or adivalent group; Z is a C1-C20 alkyl group, a C2-C20 alkenyl group, aC2-C20 alkynyl group, a C6-C20 phenyl group, a C1-C20 alkoxy group, or aC1-C20 alkyl carbonyloxy group or carboxyl group, and a hydrogen atom inany of the foregoing groups is optionally replaced by a fluorine atom,an oxygen atom, or a nitrogen atom; and O is an oxygen atom.)

In the fluorine-containing copolymer (2), Q is a C3-C10 fluoroalkylgroup and X is a carbonyl group (—C(═O)—) in the repeating unitrepresented by the formula (A), and Z is a bis(trifluoromethyl) vinylgroup (—CH═C(CF₃)₂) in the repeating unit represented by the formula(C).

Preferred combinations of the repeating unit (A) and the repeating unit(C) are listed below.

<Repeating Unit Content>

The repeating unit (A) content in terms of mol % relative to the sum ofthe repeating units (A) and (C) in the fluorine-containing copolymer (2)is preferably 5% or higher but 80% or lower, more preferably 10% orhigher but 60% or lower.

The repeating unit (C) content in terms of mol % relative to the sum ofthe repeating units (A) and (C) in the fluorine-containing copolymer ispreferably 3% or higher but 90% or lower, more preferably 5% or higherbut 80% or lower.

The fluorine-containing copolymer (2) may contain, if necessary, arepeating unit other than the repeating units (A) and (C) for thepurpose of improving the solubility in an organic solvent oradhesiveness to a substrate or hardness when formed into a film. Therepeating unit content other than the repeating units (A) and (C) interms of mol % relative to the sum of the repeating units (A) and (C) ispreferably 50% or lower, more preferably 30% or lower. The repeatingunit content other than the repeating units (A) and (C) of higher than50% tends to fail to achieve the lyophobicity.

[Fluorine-Containing Copolymer (3)]

The fluorine-containing copolymer (3) contains all of a repeating unitrepresented by the following formula (A), a repeating unit representedby the following formula (B), and a repeating unit represented by thefollowing formula (C).

(In the formulas, R¹, R², and R³ are each independently a hydrogen atom,a fluorine atom, or a C1-C20 alkyl group in which hydrogen atoms bondedto a carbon atom are optionally partly or entirely replaced by fluorineatoms; Q is a C1-C20 fluoroalkyl group optionally containing a hydrogenatom, an oxygen atom, or a nitrogen atom; X and Y are each independentlya single bond or a divalent group; Z is a C1-C20 alkyl group, a C2-C20alkenyl group, a C2-C20 alkynyl group, a C6-C20 phenyl group, a C1-C20alkoxy group, or a C1-C20 alkyl carbonyloxy group or carboxyl group, anda hydrogen atom in any of the foregoing groups is optionally replaced bya fluorine atom, an oxygen atom, or a nitrogen atom; 0 is an oxygenatom; and H is a hydrogen atom.)

In the fluorine-containing copolymer (3), preferably, Q is ahexafluoroisopropyl group (—CH(CF₃)₂) and X is a carbonyl group(—C(═O)—) in the repeating unit represented by the formula (A), Y is acarboxyethylene group (—C(═O)—O—CH₂CH₂—) in the repeating unitrepresented by the formula (B), and R³ is a hydrogen atom or a methylgroup and Z is a C1-C4 alkyl carbonyloxy group in the repeating unitrepresented by the formula (C).

Preferred combinations of the repeating unit (A), the repeating unit(B), and the repeating unit (C) are listed below.

In the fluorine-containing copolymer (3), preferably, Q is a C3-C10fluoroalkyl group and X is a carbonyl group (—C(═O)—) in the repeatingunit represented by the formula (A), Y is a p-phenylene group (—C₆H₄—),a p-phenylene carbonyl group (—C₆H₄—C(═O)—), or a p-phenylenehexafluoroisopropylene group (—C₆H₄—C(CF₃)₂—) in the repeating unitrepresented by the formula (B), and R³ is a hydrogen atom or a methylgroup and Z is a bis(trifluoromethyl)vinyl group (—CH═C(CF₃)₂) in therepeating unit represented by the formula (C).

Preferred combinations of the repeating unit (A), the repeating unit(B), and the repeating unit (C) are listed below.

<Repeating Unit Content>

The repeating unit (A) content in terms of mol % relative to the sum ofthe repeating units (A), (B), and (C) in the fluorine-containingcopolymer (3) is preferably 5% or higher but 80% or lower, morepreferably 10% or higher but 60% or lower.

The repeating unit (B) content in terms of mol % relative to the sum ofthe repeating units (A), (B), and (C) in the fluorine-containingcopolymer (3) is preferably 10% or higher but 85% or lower, morepreferably 20% or higher but 70% or lower.

The repeating unit (C) content in terms of mol % relative to the sum ofthe repeating units (A), (B), and (C) in the fluorine-containingcopolymer is preferably 3% or higher but 90% or lower, more preferably5% or higher but 80% or lower.

The fluorine-containing copolymer (3) may contain, if necessary, arepeating unit other than the repeating units (A), (B), and (C) for thepurpose of improving the solubility in an organic solvent oradhesiveness to a substrate or hardness when formed into a film. Therepeating unit content other than the repeating units (A), (B), and (C)relative to the sum of the repeating units (A), (B), and (C) ispreferably 50% or lower, more preferably 30% or lower. The repeatingunit content other than the repeating units (A), (B), and (C) of higherthan 50% tends to fail to achieve the lyophobicity.

[Molecular Weight of Fluorine-Containing Copolymer]

In the production method of a substrate with a patterned film of thepresent disclosure, the number average molecular weight Mn of thefluorine-containing copolymer, such as the fluorine-containingcopolymers (1) to (3), in the patterned film is preferably 1,000 or morebut 100,000 or less, more preferably 3,000 or more but 60,000 or less.The molecular weight dispersion Mw/Mn defined as the ratio between thenumber average molecular weight Mn and the weight average molecularweight Mw is preferably 1 or more but 4 or less, more preferably 1 ormore but 2.5 or less.

The fluorine-containing copolymer having a number average molecularweight Mn of 1,000 or more is preferred as it allows the patterned filmcontaining the fluorine-containing copolymer to have an appropriatehardness and facilitates formation of a film having a desired thickness.In addition, such a fluorine-containing copolymer is also preferred fromthe standpoint of the durability of the pattern as it facilitatesformation of a fine pattern including a lyophobic part and a lyophilicpart. The fluorine-containing copolymer having a number averagemolecular weight Mn of 100,000 or less is preferred as it is easilydissolved in a solvent upon preparation of a composition for forming apattern containing the fluorine-containing copolymer on a substrate, theobtained composition is easily applicable, and the resulting film is notlikely to suffer cracks.

The number average molecular weight Mn and weight average molecularweight Mw of the polymer are measured using a high-performance gelpermeation chromatography system (hereafter, also referred to as GPC,produced by Tosoh Corporation, type: HLC-8320GPC), an ALPHA-M column andan ALPHA-2500 column (both produced by Tosoh Corporation) connected inseries, and tetrahydrofuran (THF) as a developing solvent. The detectorused is a differential refractometer.

3. Repeating Unit

Hereinbelow, the repeating unit (A) contained in the fluorine-containingcopolymer such as the fluorine-containing copolymers (1) to (3), therepeating unit (B) contained in the fluorine-containing copolymer (1) or(3), and the repeating unit (C) contained in the fluorine-containingcopolymer (2) or (3) are described.

[Repeating Unit (A)]

(In the formula, R¹ is a hydrogen atom, a fluorine atom, or a C1-C20alkyl group in which hydrogen atoms bonded to a carbon atom areoptionally partly or entirely replaced by fluorine atoms; Q is a C1-C20fluoroalkyl group optionally containing a hydrogen atom, an oxygen atom,or a nitrogen atom; X is a single bond or a divalent group; and O is anoxygen atom.)

Examples of R¹ include a hydrogen atom, a methyl group, an ethyl group,a propyl group, an isopropyl group, a butyl group, an isobutyl group, atert-butyl group, a fluorine atom, a trifluoromethyl group, atrifluoroethyl group, a trifluoropropyl group, a1,1,1,3,3,3-hexafluoroisopropyl group (—C(CF₃)₂H), and aheptafluoroisopropyl group. R¹ is particularly preferably a hydrogenatom, a fluorine atom, or a methyl group.

Q is preferably a C3-C10 fluoroalkyl group, and examples thereof includea trifluoromethyl group, a trifluoroethyl group, a trifluoropropylgroup, a 1,1,1,3,3,3-hexafluoroisopropyl group (—C(CF₃)₂H), aheptafluoroisopropyl group, a pentafluoropropyl group, aperfluorohexylethyl group, a perfluorooctylethyl group, aperfluorodecylethyl group, a 1,2,2,3,3,4,4,5-octafluorocyclopentylmethylgroup, a perfluorocyclopentyl group, a perfluorocyclohexyl group, and aperfluoroadamanthyl group. Q is particularly preferably aperfluorohexylethyl group or a hexafluoroisopropyl group.

X is a single bond or a divalent group, and a hydrogen atom contained inthe divalent group may be replaced by a fluorine atom. The divalentgroup is preferably a C2-C10 divalent group. Examples thereof include amethylene group, a C2-C10 alkylene group, a C2-C10 alkenylene group, aC6-C10 divalent aryl group, and a C4-C10 divalent alicyclic hydrocarbongroup. The alkylene or alkenylene group may contain an ether bond (—O—),a carbonyl group (—C(═O)—), a carboxyl group (—C(═O)—O—), or anoxycarbonyl group (—O—C(═O)—). Since the divalent group having a longaliphatic chain lowers the lyophobicity, X is more preferably a singlebond, a carbonyl group (—C(═O)—), an oxyethylene group (—O—CH₂—CH₂—), acarboxyethylene group (—C(═O)—O—CH₂—CH₂—), a carboxyphenylene group(—C(═O)—O—C₆H₄—), a phenylene group (—C₆H₄—), or a phenylenehexafluoroisopropylene group (—C₆H₄—C(CF₃)₂—). X is particularlypreferably a carbonyl group.

The repeating unit (A) also preferably has a structure represented bythe following formula (4).

(In the formula (4), R⁴ and R⁵ are each independently a hydrogen atom, afluorine atom, or a C1-C3 alkyl group in which hydrogen atoms bonded toa carbon atom are optionally partly or entirely replaced by fluorineatoms; 0 is an oxygen atom; H is a hydrogen atom; and F is a fluorineatom.)

[Repeating Unit (B)]

(In the formula, R² is a hydrogen atom, a fluorine atom, or a C1-C20alkyl group in which hydrogen atoms bonded to a carbon atom areoptionally partly or entirely replaced by fluorine atoms; Y is a singlebond or a divalent group; 0 is an oxygen atom; and H is a hydrogenatom.)

R² is preferably a hydrogen atom, a methyl group, an ethyl group, apropyl group, an isopropyl group, a butyl group, an isobutyl group, atert-butyl group, a fluorine atom, a trifluoromethyl group, atrifluoroethyl group, a trifluoropropyl group, a1,1,1,3,3,3-hexafluoroisopropyl group (—C(CF₃)₂H), or aheptafluoroisopropyl group. R² is particularly preferably a hydrogenatom, a fluorine atom, or a methyl group.

Y is a single bond or a divalent group. The divalent group is preferablya C2-C10 divalent group, and examples thereof include a methylene group,a C2-C10 alkylene group, a C2-C10 alkenylene group, a C6-C10 arylenegroup, and a C4-C10 divalent alicyclic hydrocarbon group. The alkyleneor alkenylene group may contain an ether bond (—O—), a carbonyl group(—C(═O)—), a carboxyl group (—C(═O)—O—), or an oxycarbonyl group(—O—C(═O)—). Since the divalent group having a long aliphatic chainlowers the lyophobicity, Y is preferably a single bond, a carbonyl group(—C(═O)—), an oxyethylene group (—O—CH₂—CH₂—), a carboxyethylene group(—C(═O)—O—CH₂—CH₂—), a carboxyphenylene group (—C(═O)—O—C₆H₄—), aphenylene group (—C₆H₄—), or a phenylene hexafluoroisopropylene group(—C₆H₄—C(CF₃)₂—). Particularly preferred is a p-phenylene group or acarboxyethylene group.

[Repeating Unit (C)]

(In the formula, R³ is a hydrogen atom, a fluorine atom, or a C1-C20alkyl group in which hydrogen atoms bonded to a carbon atom areoptionally partly or entirely replaced by fluorine atoms; and Z is aC1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, aC6-C20 phenyl group, a C1-C20 alkoxy group, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and a hydrogen atom in any of theforegoing groups is optionally replaced by a fluorine atom, an oxygenatom, or a nitrogen atom.)

R³ is preferably a hydrogen atom, a methyl group, an ethyl group, apropyl group, an isopropyl group, a butyl group, an isobutyl group, atert-butyl group, a fluorine atom, a trifluoromethyl group, atrifluoroethyl group, a trifluoropropyl group, a1,1,1,3,3,3-hexafluoroisopropyl group (—C(CF₃)₂H), or aheptafluoroisopropyl group. R³ is particularly preferably a hydrogenatom, a fluorine atom, or a methyl group.

Z is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynylgroup, a C6-C20 phenyl group, a C1-C20 alkoxy group, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and a hydrogen atom in any of theforegoing groups is optionally replaced by a fluorine atom, an oxygenatom, or a nitrogen atom. For obtaining a high effect of recoveringlyophobicity by heating, Z is particularly preferably abis(trifluoromethyl)vinyl group (—CH═C(CF₃)₂).

4. Synthesis of Fluorine-Containing Copolymers (1) to (3) 4-1. Monomer

Hereinbelow, a monomer (A1) providing a repeating unit (A), a monomer(B1) providing a repeating unit (B), and a monomer (C1) providing arepeating unit (C) are mentioned.

The fluorine-containing copolymer (1) is obtainable by copolymerizationof a monomer (A1) and a monomer (B1). The fluorine-containing copolymer(2) is obtainable by copolymerization of a monomer (A1) and a monomer(C1). The fluorine-containing copolymer (3) is obtainable bycopolymerization of a monomer (A1), a monomer (B1), and a monomer (C1).

(R¹, X, and Q are each the same as defined for the formula (A).)

(R² and Y are each the same as defined for the formula (B).)

Examples of the monomer (B1) include the following monomers. Asdescribed above, R² is particularly preferably a hydrogen atom, afluorine atom, or a methyl group.

(R³ and Z are each the same as defined for the formula (C).)

4-2. Synthesis Method of Fluorine-Containing Copolymers (1) to (3)

The fluorine-containing copolymers (1) to (3) can be synthesized by acommon polymerization method using the monomers (A1), (B1), and (C1) asraw materials. Preferred are radical polymerization and ionpolymerization. In some cases, coordinated anionic polymerization,living anionic polymerization, or cationic polymerization may beselected. A polymerization solvent may be used in the polymerization.Hereinbelow, radical polymerization is described.

Radical polymerization can be carried out in the presence of a radicalpolymerization initiator or a radical polymerization initiating sourceby a known polymerization method such as bulk polymerization, solutionpolymerization, suspension polymerization, or emulsion polymerization bybatch operation, semi-continuous operation, or continuous operation.

<Radical Polymerization Initiator>

Examples of the radical polymerization initiator include azo compounds,peroxide compounds, and redox compounds. Examples of the azo compoundsinclude azobisisobutyronitrile. Examples of the peroxide compoundsinclude t-butyl peroxypivalate, di-t-butyl peroxide, i-butyryl peroxide,lauroyl peroxide, succinic peroxide, dicinnamyl peroxide, di-n-propylperoxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide,hydrogen peroxide, and ammonium persulfate. The redox compound may be acompound obtained by combining an oxidant and a reducing agent. Examplesthereof include a compound obtained by combining hydrogen peroxide waterwith a divalent iron ion (Fenton's reagent).

<Polymerization Solvent>

The polymerization solvent is preferably those not inhibiting radicalpolymerization, and examples thereof include ester solvents, ketonesolvents, hydrocarbon solvents, and alcohol solvents. Also usable arewater, ether solvents, cyclic ether solvents, freon solvents, andaromatic solvents.

Specific examples of the polymerization solvent include ethyl acetateand n-butyl acetate as the ester solvents, acetone and methyl isobutylketone as the ketone solvents, toluene and cyclohexane as thehydrocarbon solvents, and methanol, isopropyl alcohol, and ethyleneglycol monomethyl ether as the alcohol solvents.

Each of these polymerization solvents may be used alone, or in admixtureof two or more. A molecular weight modifier such as mercaptan may beused together.

<Polymerization Condition>

The polymerization temperature may be appropriately determined inaccordance with the type of the radical polymerization initiator or theradical polymerization initiating source. The radical polymerizationinitiator or the radical polymerization initiating source is preferablyselected as appropriate so that the polymerization temperature is setto, for example, 20° C. or higher but 200° C. or lower, preferably 30°C. or higher but 140° C. or lower. The molecular weights of thefluorine-containing copolymers (1) to (3) can be controlled by the typeof the radical polymerization initiator or the radical polymerizationinitiating source and adjustment of the polymerization conditions.

The polymerization solvent such as an organic solvent or water isremoved from the solutions or dispersions containing thefluorine-containing copolymers (1) to (3) after polymerization by aknown method such as reprecipitation, filtration, or distillation underreduced pressure.

In the case of using the fluorine-containing copolymers (1) to (3) as aresist component, the solubility of the fluorine-containing copolymers(1) to (3) in a developing solution varies in accordance with themolecular weights of the fluorine-containing copolymers (1) to (3),which may change the patterning conditions in lithography. Largermolecular weights of the fluorine-containing copolymers (1) to (3) tendto lower the dissolution speeds thereof in a developing solution andsmaller molecular weights of the fluorine-containing copolymers (1) to(3) tend to increase the dissolution speeds. The molecular weights ofthe fluorine-containing copolymers (1) to (3) can be controlled byadjusting the polymerization conditions.

5. Composition for Forming a Resist Pattern

A fluorine-containing copolymer such as the fluorine-containingcopolymers (1) to (3) is blended with a photosensitizer or acidgenerating agent, a basic compound, and a solvent to obtain acomposition for forming a resist pattern. The obtained composition forforming a resist pattern is applied to a substrate, followed bypatterning by lithography. Thus, a substrate with a patterned film usedin the production method of a substrate with a patterned film of thepresent disclosure can be obtained. Hereinbelow, the composition forforming a resist pattern is also simply referred to as a resist.

The resist essentially contains a fluorine-containing copolymer (a) suchas the fluorine-containing copolymers (1) to (3), and contains as neededan alkali-soluble resin (b), a naphthoquinonediazide group-containingcompound (c), a solvent (d), a photoacid generator (e), a basic compound(f), and a crosslinking agent (g).

5-1. Alkali-Soluble Resin (b)

Examples of the alkali-soluble resin (b) include an alkali-solublenovolak resin. The alkali-soluble novolak resin can be obtained bycondensation of a phenol compound and an aldehyde in the presence of anacid catalyst.

<Phenol Compound>

Examples of the phenol compound include phenol, o-cresol, m-cresol,p-cresol, 2,3-dimethyl phenol, 2,4-dimethyl phenol, 2,5-dimethyl phenol,3,4-dimethyl phenol, 3,5-dimethyl phenol, 2,3,5-trimethyl phenol,3,4,5-trimethyl phenol, resorcinol, 2-methyl resorcinol, 4-ethylresorcinol, hydroquinone, methyl hydroquinone, catechol,4-methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol.Each of these phenol compounds may be used alone or in combination oftwo or more.

<Aldehyde>

Examples of the aldehyde include formaldehyde, trioxane,paraformaldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, α-phenyl propyl aldehyde, β-phenyl propyl aldehyde,o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde,o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde,nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde,terephthalaldehyde, and isophthalaldehyde.

<Acid Catalyst>

Examples of the acid catalyst include hydrochloric acid, nitric acid,sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalicacid, acetic acid, methanesulfonic acid, diethyl sulfuric acid, andp-toluene sulfonic acid. Each of these acid catalysts may be used aloneor in combination of two or more thereof.

The mass average molecular weight of the alkali-soluble resin (b)component is preferably 1,000 to 50,000 from the standpoint of thedevelopability and resolution of the positive resist composition.

5-2. Naphthoquinonediazide Group-Containing Compound (c)

The naphthoquinonediazide group-containing compound (c) is not limited,and those used as a photosensitive element of an i-line resistcomposition. Examples thereof include a naphthoquinone-1,2-diazidesulfonic acid ester compound, ortho-benzoquinonediazide sulfonic acidester, ortho-anthraquinonediazide sulfonic acid ester, an ester compoundof a naphthoquinone-1,2-diazide sulfonyl halide and a hydroxy compound.Examples of the naphthoquinone-1,2-diazide sulfonyl halide includenaphthoquinone-1,2-diazide-5-sulfonyl chloride,naphthoquinone-1,2-diazide-4-sulfonyl chloride, andnaphthoquinone-1,2-diazide-6-sulfonyl chloride.

The naphthoquinonediazide group-containing compound (c) is preferablynaphthoquinonediazide-4-sulfonic acid ester,naphthoquinonediazide-5-sulfonic acid ester, ornaphthoquinonediazide-6-sulfonic acid ester for its excellentsolubility. Each of these compounds may be used alone or in admixture oftwo or more thereof.

The amount of the naphthoquinonediazide group-containing compound (c) ispreferably 10% by mass or more but 60% by mass or less, more preferably20% by mass or more but 50% by mass or less, relative to the total massof the alkali soluble resin (b) and the naphthoquinonediazidegroup-containing compound (c). If the amount is more than 60% by mass,the resulting composition fails to have sensitivity as a resist. If theamount is less than 10% by mass, a fine pattern is not likely to beobtained due to factors such as film reduction in an unexposed partafter photolithography.

5-3. Solvent (d)

The solvent (d) contained in the resist may be selected from knownsolvents for a resist which can dissolve the fluorine-containingcopolymer (a) such as the fluorine-containing copolymers (1) to (3), thealkali soluble resin (b), and the naphthoquinonediazide group-containingcompound (c) to provide a homogeneous solution. Two or more solvents maybe used in admixture.

Examples of such a solvent include ketones, alcohols, polyhydricalcohols, esters, aromatic solvents, ethers, and fluorine solvents. Theexamples further include high-boiling-point solvents with an aim ofimproving the applicability, such as turpentine-based petroleum naphthasolvents and paraffin-based solvents.

Examples of the ketones include acetone, methyl ethyl ketone,cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl isopentylketone, and 2-heptanone. Examples of the alcohols include isopropanol,butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol,4-methyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-pentanol,n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amylalcohol,t-amylalcohol, isoamylalcohol, 2-ethyl-1-butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol. Examples of the polyhydric alcohols includeethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether(EDC), diethylene glycol monoacetate, propylene glycol monoacetate,dipropylene glycol monoacetate, propylene glycol monoethyl ether,propylene glycol monopropyl ether, propylene glycol monobutyl ether,propylene glycol monomethyl ether acetate (PGMEA), propylene glycolmonomethyl ether (PGME), and derivatives of these polyhydric alcohols.Examples of the esters include methyl lactate, ethyl lactate (EL),methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethylpyruvate, methyl methoxypropionate, ethyl ethoxypropionate, andγ-butyrolactone (GBL). Examples of the aromatic solvents include tolueneand xylene. Examples of the ethers include diethyl ether, dioxane,anisole, and diisopropylether. Examples of the fluorine solvents includehexafluoroisopropyl alcohol.

The solvent is preferably ethylene glycol dimethyl ether (EDC),propylene glycol monomethyl ether acetate (PGMEA), propylene glycolmonomethyl ether (PGME), cyclohexanone, ethyl lactate (EL), orγ-butyrolactone (GBL).

With regard to the amount of the solvent (d) contained in the resist,the resist preferably has a solid content of 1% by mass or higher but25% by mass or lower, more preferably 5% by mass or higher but 15% bymass or lower. Adjustment of the solid content of the resist can controlthe thickness of the resin film to be formed.

5-4. Photoacid Generator (e)

The photoacid generator (e) may be any compound that is used as an acidgenerator for a chemically amplified resist. Examples thereof includesulfonates and sulfonic acid esters.

Examples of the sulfonates include iodonium sulfonate, sulfoniumsulfonate, N-imide sulfonate, N-oxime sulfonate, o-nitrobenzylsulfonate, tris(methane) sulfonate of pyrogallol, triphenyl sulfoniumtrifluoromethane sulfonate, and triphenyl sulfonium perfluoro-n-butanesulfonate.

During the exposure in photolithography, these photoacid generatorsgenerate alkanesulfonic acid, arylsulfonic acid, or partially- orcompletely fluorinated arylsulfonic acid or alkanesulfonic acid. Thephotoacid generator generating completely fluorinated alkanesulfonicacid is preferred. Preferred examples thereof include triphenylsulfonium trifluoromethane sulfonate and triphenyl sulfoniumperfluoro-n-butane sulfonate.

5-5. Basic Compound (f)

The basic compound (f) has an effect of lowering the diffusion rate ofthe acid generated by the photoacid generator (e) in the resist film.Addition of the basic compound (f) is expected to improve the shape ofthe resist pattern by adjusting the acid diffusion distance and toimprove the stability of imparting the resist pattern having a desiredaccuracy even when the time elapsed from formation of the resist film toexposure is long.

Examples of such a basic compound include aliphatic amines, aromaticamines, heterocyclic amines, and aliphatic polycyclic amines. Preferredare secondary or tertiary aliphatic amines and alkyl alcohol amines.Examples of such amines include trimethylamine, triethylamine,tripropylamine, tributylamine, tripentylamine, trihexylamine,triheptylamine, trioctylamine, trinonylamine, tridecylamine,tridodecylamine, dimethylamine, diethylamine, dipropylamine,dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine,dinonylamine, didecylamine, didodecylamine, dicyclohexylamine,methylamine, ethylamine, propylamine, butylamine, pentylamine,hexylamine, heptylamine, octylamine, nonylamine, decylamine,dodecylamine, diethanolamine, triethanolamine, diisopropanolamine,triisopropanolamine, dioctanolamine, trioctanolamine, aniline, pyridine,picoline, lutidine, bipyridine, pyrrole, piperidine, piperazine, indole,and hexamethylenetetramine. Each of these basic compounds may be usedalone or in combination of two or more.

The amount of the basic compound (f) in the resist is preferably 0.001to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to100 parts by mass of the fluorine-containing copolymer (a) such as thefluorine-containing copolymers (1) to (3). The basic compound (f) in anamount of less than 0.001 parts by mass fails to sufficiently provide aneffect as an additive. The basic compound (f) in an amount of more than2 parts by mass may lower the resolution property and sensitivity.

5-6. Crosslinking Agent (g)

The resist may contain a crosslinking agent (g) as needed. A known agentmay be used as the crosslinking agent (g). Examples of the crosslinkingagents include 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine(methylol melamine curing agent) and its derivatives,1,3,4,6-tetrakis(methoxymethyl)glycoluril (glycoluril curing agent) andits derivatives, polyfunctional epoxy compounds, polyfunctional oxetanecompounds, and polyfunctional isocyanate compounds. Multiple types ofcrosslinking agents may be used.

6. Formation of Pattern

Formation of a pattern in the production method of a substrate with apatterned film of the present disclosure is described. Formation of apattern includes: a film-forming step in which the resist is appliedonto a substrate to form a film; an exposure step in which the film isexposed to an electron magnetic wave or electron beam having awavelength of 600 nm or shorter through a photomask so that thephotomask pattern is transferred to the film; and a development step inwhich the film is developed using a developing solution to obtain apattern.

A pattern can be formed using a resist containing a fluorine-containingcopolymer such as the fluorine-containing copolymers (1) to (3), througha film-forming step (a) in which the resist is applied onto a substrateto form a resist film; an exposure step (b) in which the resist film isheated and then exposed to an electron magnetic wave or electron beamhaving a wavelength of 600 nm or shorter through a patterned photomask;and a development step (c) in which the exposed resist film is developedusing an alkali developing solution or an organic solvent to obtain aresist pattern that is a pattern transferred from the photomask on thesubstrate.

Hereinbelow, each step is described with reference to examples.

6-1. Film-Forming Step (a)

In the film-forming step (a), the resist containing afluorine-containing copolymer, such as the fluorine-containingcopolymers (1) to (3), is applied to a substrate such as a silicon waferby spin coating, and the silicon wafer is heated on a hot plate at 60°C. or higher but 200° C. or lower for 10 seconds or longer but 10minutes or shorter, preferably at 80° C. or higher but 150° C. or lowerfor 30 seconds or longer but two minutes or shorter. Thus, a resist filmis formed on the substrate.

The substrate may be, for example, a silicon wafer, a metal substrate,or a glass substrate. An organic or inorganic film may be provided onthe substrate. For example, an anti-reflection film or an underlayer ofa multilayer resist may be provided, and a pattern may be formed on thatfilm.

6-2. Exposure Step (b)

In the exposure step (b), a photomask is set on an exposure device, andthe resist film is irradiated with an electromagnetic wave or anelectron beam having a wavelength of 600 nm or shorter to an exposuredose of, for example, 1 mJ/cm² or more but 200 mJ/cm² or less,preferably 10 mJ/cm² or more but 100 mJ/cm² or less, through thephotomask, followed by heating of the resist film on a hot plate at, forexample, 60° C. or higher but 150° C. or lower for 10 seconds or longerbut five minutes or shorter, preferably at 80° C. or higher but 130° C.or lower for 30 seconds or longer but three minutes or shorter. Thus,the pattern of the photomask is transferred to the resist film.

The electromagnetic wave has a wavelength of preferably 100 to 600 nm,more preferably 300 to 500 nm. In particular, light containing i-line(365 nm), h-line (405 nm), or g-line (436 nm) is preferred. Ifnecessary, light having a wavelength of 330 nm or shorter may be cutoff.

The light source may be, for example, KrF excimer laser (wavelength: 248nm), ArF excimer laser (wavelength: 193 nm), or F2 excimer laser(wavelength: 157 nm).

6-3. Development Step (c)

In the development step (c), either an exposed part or an unexposed partof the resist film is dissolved using a developing solution such as anaqueous solution of tetramethyl ammonium hydroxide (TMAH) at aconcentration of, for example, 0.1% by mass or higher but 5% by mass orlower, preferably 2% by mass or higher but 3% by mass or lower, or anorganic solvent, thereby forming a pattern. Thus, a patterned film isobtained on the substrate. Examples of the organic solvent includepropylene glycol monomethyl ether acetate (PGMEA) and butyl acetate. Inthe development step, a substrate with a patterned film having a targetpattern can be obtained by bringing the resist film into contact withthe developing solution, for example, for 10 seconds or longer but threeminutes or shorter, preferably 30 seconds or longer but two minutes orshorter, by a known method such as dipping, puddling, or spraying.

Examples

The production method of a substrate with a patterned film of thepresent disclosure is specifically described based on the followingexamples. The present invention is not intended to be limited to thefollowing examples.

1. Synthesis of Monomer

Fluorine-containing monomers for obtaining the fluorine-containingcopolymers (1) to (3) were synthesized.

1-1. Synthesis of MA-CH2-OFCP Synthesis of1,2,2,3,3,4,4,5-octafluorocyclopentanemethanol

In nitrogen atmosphere, a 300-ml stainless steel pressure-resistantcontainer was charged with 31.5 ml (0.75 mol) of methanol, 1.11 g(0.0045 mol) of benzoyl peroxide (BPO), and 31.2 g (0.12 mol) ofoctafluorocyclopentene (produced by Central Glass Co., Ltd.) at roomtemperature (20° C.: the same applies hereinafter) and sealed. Thecontents were heated to 120° C. and then stirred for 24 hours, followedby the reaction below. After cooling of the container, the contents weresubjected to atmospheric distillation, whereby 28.8 g of1,2,2,3,3,4,4,5-octafluorocyclopentanemethanol was obtained at a yieldof 80%.

The results of nuclear magnetic resonance (NMR) analysis are shownbelow.

<NMR Analysis Results>

1H-NMR (CDCl₃, TMS reference)

δ (ppm): 4.21-4.05 (2H, m), 5.22 (1H, m)

Synthesis of MA-CH2-OFCP

To a 300-ml glass flask equipped with a stirrer were collected 24.3 g(0.1 mol) of 1,2,2,3,3,4,4,5-octafluorocyclopentanemethanol obtained inthe above synthesis, 15.1 g (0.15 mol) of triethylamine, andmethoxyphenol (1000 ppm) as a polymerization inhibitor. To the reactionsystem was added dropwise 16.9 g (0.11 mol) of methacrylic acidanhydride at 30° C., followed by stirring for two hours. After thestirring, 40 ml of diisopropylether and 30 ml of pure water were addedto the system, followed by separation. Then, 20 ml of 1% by mass aqueoussodium hydroxide was added, stirred for one hour, and transferred to aseparatory funnel. Thus, an organic layer was obtained. The organiclayer was washed twice using 30 ml of pure water, and subjected todistillation under reduced pressure at a pressure of 1.0 kPa and atemperature of 70° C. to 72° C., whereby 26.5 g of MA-CH2-OFCP shownbelow was obtained at a yield of 85%.

<NMR Analysis Results>

¹H-NMR (solvent: deuterochloroform, reference material: TMS), δ (ppm):1.92 (3H, s), 4.21-4.05 (2H, m), 5.22 (1H, m), 5.65 (1H, q), 6.12 (1H,q)

1-2. Synthesis of 1,1-bis(trifluoromethyl)butadiene (BTFBE)

An amount of 400 g of concentrated sulfuric acid in a 1000-ml glassflask equipped with a stirrer was heated to 100° C., and 300 g of1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol was gradually addeddropwise thereto over one hour to cause the following reaction. Afteraddition of sodium hydrogen carbonate to the reaction system, a fractionat 68° C. to 70° C. was recovered by atmospheric distillation, whereby1,1-bis(trifluoromethyl)butadiene (BTFBE) was obtained at a yield of58%.

<NMR analysis results>¹H-NMR (solvent: deuterochloroform, referencematerial: TMS), δ (ppm): 5.95 (1H, dd), 6.05 (1H, dd), 6.85 (1H, m),7.04 (1H, m) ¹⁹F-NMR (solvent: deuterochloroform, reference material:COD), δ (ppm): −58.4 (3F, m), −65.3 (3F, m)

2. Synthesis of Polymer [Measurement of Molar Ratio of Repeating Units]NMR

The molar ratio of the repeating units in the polymer was determinedfrom the measurement values of ¹H-NMR and ¹⁹F-NMR by NMR.

[Measurement of Molecular Weight of Polymer] GPC

The number average molecular weight Mn and the weight average molecularweight Mw of the polymer were measured using a high-performance gelpermeation chromatography system (produced by Tosoh Corporation, type:HLC-8320GPC), an ALPHA-M column and an ALPHA-2500 column (both producedby Tosoh Corporation) connected in series, and tetrahydrofuran (THF) asa developing solvent. The detector used was a differentialrefractometer. The molecular weight dispersion Mw/Mn was calculatedbased on the number average molecular weight Mn and the weight averagemolecular weight Mw.

2-1. Synthesis of Fluorine-Containing Copolymer 1

To a 300-ml glass flask equipped with a stirrer were collected 43.2 g(0.1 mol) of 2-(perfluorohexyl)ethyl methacrylate (MA-C6F), 19.0 g (0.1mol) of BTFBE, and 62 g of THF as a solvent at room temperature, and 0.8g (0.005 mol) of α,α′-azobisisobutyronitrile (AIBN) as a polymerizationinitiator was further added, followed by deaeration with stirring. Afterpurging the atmosphere inside the flask with nitrogen gas, the contentswere heated to a temperature of 75° C. and reacted for six hours. Afterdecompression of the reaction system to remove THF, the reaction systemwas added dropwise to 300 g of n-heptane, whereby a clear viscoussubstance was precipitated. A supernatant of the viscous substance wasseparated by decantation. The viscous substance was dried under reducedpressure at a temperature of 60° C., whereby 22 g of afluorine-containing copolymer 1 in the form of a clear viscous substancewas obtained at a yield of 37%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 1 in terms of the molar ratio was (MA-C6F-derived repeatingunit):(BTFBE-derived repeating unit)=28:72.

<GPC Measurement Results>

Mw=7,300, Mw/Mn=1.4

2-2. Synthesis of Fluorine-Containing Copolymer 2

To a 300-ml glass flask equipped with a stirrer were collected 43.2 g(0.1 mol) of MA-C6F, 27.0 g (0.1 mol) of1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)propan-2-ol (4-HFA-St), 19.0 g(0.1 mol) of BTFBE, and 90 g of THF at room temperature, and 0.8 g(0.005 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to a temperature of 75° C. and reacted forsix hours. After removal of THF by vacuum concentration of the solutionafter completion of the reaction, the reaction system was added dropwiseto 350 g of n-heptane, whereby a clear viscous substance wasprecipitated. A supernatant of the viscous substance was separated bydecantation. The viscous substance was dried under reduced pressure at atemperature of 60° C., whereby 48 g of a fluorine-containing copolymer 2in the form of a clear viscous substance was obtained at a yield of 52%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 2 in terms of the molar ratio was (MA-C6F-derived repeatingunit):(4-HFA-St-derived repeating unit):(BTFBE-derived repeatingunit)=17:37:46.

<GPC Measurement Results>

Mw=13,300, Mw/Mn=1.3

2-3. Synthesis of Fluorine-Containing Copolymer 3

To a 300-ml glass flask equipped with a stirrer were collected 43.2 g(0.1 mol) of MA-C6F, 16.2 g (0.1 mol) of p-acetoxystyrene (AcO-St), 19.0g (0.1 mol) of BTFBE, and 80 g of THF at room temperature, and 0.8 g(0.005 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to a temperature of 75° C. and reacted forsix hours. After decompression of the reaction system to remove THF, 350g of n-heptane was added dropwise to the reaction system, whereby aclear viscous substance was precipitated. A supernatant of the viscoussubstance was separated by decantation. The viscous substance wasdissolved in 100 g of methanol, and 10.1 g (0.1 mol) of triethylamine(TEA) was added thereto. The solution was heated to 50° C. and stirredfor eight hours for solvolysis of an acetoxy group. After elimination ofthe acetoxy group was confirmed, the solution was concentrated and driedunder reduced pressure at a temperature of 60° C., whereby 35 g of afluorine-containing copolymer 3 in the form of a white solid wasobtained at a yield of 55%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 3 in terms of the molar ratio was (MA-C6F-derived repeatingunit):(p-hydroxystyrene (p-HO-St)-derived repeating unit):(BTFBE-derivedrepeating unit)=12:38:50.

<GPC Measurement Results>

Mw=17,500, Mw/Mn=1.4

2-4. Synthesis of Fluorine-Containing Copolymer 4

A fluorine-containing copolymer 4 containing the following repeatingunits was synthesized in the same manner as in synthesis of thefluorine-containing copolymer 3 described above, except that MA-C6F usedin synthesis of the fluorine-containing copolymer 3 was replaced byhexafluoroisopropyl methacrylate (HFIP-M). The fluorine-containingcopolymer 4 was obtained at a yield of 51%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 4 in terms of the molar ratio was (HFIP-M-derived repeatingunit):(p-HO-St-derived repeating unit):(BTFBE-derived repeatingunit)=15:39:46.

<GPC Measurement Results>

Mw=15,200, Mw/Mn=1.4

2-5. Synthesis of Fluorine-Containing Copolymer 5

A fluorine-containing copolymer 5 containing the following repeatingunits was synthesized in the same manner as in synthesis of thefluorine-containing copolymer 3 described above, except that MA-C6F usedin synthesis of the fluorine-containing copolymer 3 was replaced byMA-CH2-OFCP. The fluorine-containing copolymer 5 was obtained at a yieldof 54%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 5 in terms of the molar ratio was (MA-CH2-OFCP-derivedrepeating unit):(p-HO-St-derived repeating unit):(BTFBE-derivedrepeating unit)=13:38:49.

<GPC Measurement Results>

Mw=16,100, Mw/Mn=1.5

2-6. Synthesis of Fluorine-Containing Copolymer 6

A fluorine-containing copolymer 6 containing the following repeatingunits was synthesized in the same manner as in synthesis of thefluorine-containing copolymer 3 described above, except that MA-C6F usedin synthesis of the fluorine-containing copolymer 3 was replaced by2-(perfluorohexyl)ethyl vinyl ether (V-C6F). The fluorine-containingcopolymer 6 was obtained at a yield of 41%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 6 in terms of the molar ratio was (V-C6F-derived repeatingunit):(p-HO-St-derived repeating unit):(BTFBE-derived repeatingunit)=10:38:52.

<GPC Measurement Results>

Mw=11,900, Mw/Mn=1.4

2-7. Synthesis of Fluorine-Containing Copolymer 7

To a 1000-ml glass flask equipped with a stirrer were collected 80.9 g(0.34 mol) of HFIP-M, 19.1 g (0.14 mol) of 2-hydroxyethyl methacrylate(HEMA), and 200 g of 2-butanone as a solvent at room temperature, and1.6 g (0.01 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to 80° C. and reacted for six hours. Afterdecompression of the reaction system to remove 2-butanone, the reactionsystem was added dropwise to 500 g of n-heptane, whereby a white solidwas precipitated. After filtration, the residue was dried under reducedpressure at 60° C., whereby 80.1 g of a fluorine-containing copolymer 7in the form of a white solid was obtained at a yield of 80%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 7 in terms of the molar ratio was (HFIP-M-derived repeatingunit):(HEMA-derived repeating unit)=68:32.

<GPC Measurement Results>

Mw=16,600, Mw/Mn=1.7

2-8. Synthesis of Fluorine-Containing Copolymer 8

To a 1000-ml glass flask equipped with a stirrer were collected 74.1 g(0.31 mol) of HFIP-M, 16.5 g (0.12 mol) of HEMA, 9.5 g (0.11 mol) ofvinyl acetate (VAc), and 50 g of butyl acetate at room temperature, and1.6 g (0.01 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to 80° C. and reacted for six hours. Afterdecompression of the reaction system to remove butyl acetate, thereaction system was added dropwise to 500 g of n-heptane, whereby awhite solid was precipitated. After filtration, the residue was driedunder reduced pressure at 60° C., whereby 85.7 g of afluorine-containing copolymer 8 in the form of a white solid wasobtained at a yield of 78%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 8 in terms of the molar ratio was (HFIP-M-derived repeatingunit):(HEMA-derived repeating unit):(VAc-derived repeatingunit)=68:25:7.

<GPC Measurement Results>

Mw=55,500, Mw/Mn=2.1

2-9. Synthesis of Fluorine-Containing Copolymer 9

To a 300-ml glass flask equipped with a stirrer were collected 84.6 g(0.2 mol) of MA-C6F, 31.7 g (0.2 mol) of p-acetoxystyrene (AcO-St), 11.2g (0.06 mol) of BTFBE, and 127 g of THF at room temperature, and 2.2 g(0.0135 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to a temperature of 70° C. and reacted forsix hours. After decompression of the reaction system to remove THF, 850g of n-heptane was added dropwise to the reaction system, whereby aclear viscous substance was precipitated. A supernatant of the viscoussubstance was separated by decantation. The viscous substance wasdissolved in 100 g of methanol, and 10.1 g (0.1 mol) of triethylamine(TEA) was added thereto. The solution was heated to 50° C. and stirredfor eight hours for solvolysis of an acetoxy group. After elimination ofthe acetoxy group was confirmed, the solution was concentrated and driedunder reduced pressure at a temperature of 60° C., whereby 95 g of afluorine-containing copolymer 9 in the form of a white solid wasobtained at a yield of 86%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 9 in terms of the molar ratio was (MA-C6F-derived repeatingunit):(p-HO-St-derived repeating unit):(BTFBE-derived repeatingunit)=30:50:20.

<GPC Measurement Results>

Mw=7,500, Mw/Mn=1.4

2-10. Synthesis of Fluorine-Containing Copolymer 10

To a 300-ml glass flask equipped with a stirrer were collected 110.5 g(0.26 mol) of MA-C6F, 45.9 g (0.31 mol) of vinylbenzoic acid (VBA), 16.0g (0.09 mol) of BTFBE, and 340 g of ethyl methyl ketone (MEK), and 10.8g (0.065 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to a temperature of 75° C. and reacted forsix hours. After decompression of the reaction system to remove MEK,1350 g of n-heptane was added dropwise to the reaction system, whereby awhite precipitate was obtained. After filtration, the residue was driedunder reduced pressure at 60° C., whereby 146.2 g of afluorine-containing copolymer 10 in the form of a thick white solid wasobtained at a yield of 85%.

<NMR Measurement Results>

The content ratio of the repeating units in the fluorine-containingcopolymer 10 in terms of the molar ratio was (MA-C6F-derived repeatingunit):(VBA-derived repeating unit):(BTFBE-derived repeatingunit)=30:50:20.

<GPC Measurement Results>

Mw=8,000, Mw/Mn=1.4

3. Synthesis of Comparative Polymer 3-1. Synthesis of ComparativePolymer 1

To a 300-ml glass flask equipped with a stirrer were collected 236.2 g(1 mol) of HFIP-M and 450 g of butyl acetate at room temperature, and 8g (0.05 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to 80° C. and reacted for six hours. Thereaction system was added dropwise to 500 g of n-heptane, whereby awhite precipitate was obtained. After filtration, the residue was driedunder reduced pressure at 60° C., whereby 165 g of a comparative polymer1 containing a HFIP-M-derived repeating unit alone, in the form of awhite solid, was obtained at a yield of 70%.

<GPC Measurement Results>

Mw=11,200, Mw/Mn=1.4

3-2. Synthesis of Comparative Polymer 2

To a 300-ml glass flask equipped with a stirrer were collected 43.2 g(0.1 mol) of MA-C6F and 85 g of butyl acetate at room temperature, and0.8 g (0.005 mol) of AIBN was further added, followed by deaeration withstirring. After purging the atmosphere inside the flask with nitrogengas, the contents were heated to 80° C. and reacted for six hours. Thecontents were added dropwise to 500 g of n-heptane, whereby a whiteprecipitate was obtained. After filtration, the residue was dried underreduced pressure at 60° C., whereby 32 g of a comparative polymer 2containing a MA-C6F-derived repeating unit, in the form of a whitesolid, was obtained at a yield of 74%.

<GPC Measurement Results>

Mw=13,800, Mw/Mn=1.6

3-3. Synthesis of Comparative Polymer 3

To a 300-ml glass flask equipped with a stirrer were collected 23.6 g(0.1 mol) of HFIP-M, 43.2 g (0.1 mol) of MA-C6F, and 130 g of butylacetate at room temperature, and 0.8 g (0.005 mol) of AIBN was furtheradded, followed by deaeration with stirring. After purging theatmosphere inside the flask with nitrogen gas, the contents were heatedto 80° C. and reacted for six hours. The contents after completion ofthe reaction were added dropwise to 500 g of n-heptane, whereby a whiteprecipitate was obtained. After filtration, the residue was dried underreduced pressure at 60° C., whereby 53 g of a comparative polymer 3 inthe form of a white solid was obtained at a yield of 80%.

<NMR Measurement Results>

The content ratio of the repeating units in the comparative polymer 3 interms of the molar ratio is (HFIP-M-derived repeatingunit):(MA-C6F-derived repeating unit)=51:49.

<GPC Measurement Results>

Mw=14,700, Mw/Mn=1.7

3-4. Synthesis of Comparative Polymer 4

The following synthesis was carried out based on Synthesis Example 6 ofPatent Literature 4.

To a 300-ml glass flask equipped with a stirrer were collected 2.50 g ofa condensate of 4-hydroxyphenyl methacrylate and1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (HPMA-QD), 0.70 g ofmethacrylic acid (MAA), 5.26 g of MA-C6F, 2.58 g of methacryloxypropyltris(trimethylsiloxy)silane (MA-P-TTMS), 1.46 g of N-cyclohexylmaleimide(N-CyM), and 51.3 g of cyclohexanone at room temperature, and 0.33 g ofAIBN was further added, followed by stirring at 110° C. for 20 hours.Thus, a comparative polymer 4 containing the following repeating unitsand having a solid content of 20% by mass was obtained.

<GPC Measurement Results>

Mw=11,000, Mw/Mn=1.5

3-5. Synthesis of Comparative Polymer 5

To a 300-ml glass flask equipped with a stirrer were collected 7.2 g(0.083 mol) of methacrylic acid (MAA), 9.6 g (0.022 mol) of MA-C6F, 7.2g (0.055 mol) of 2-hydroxyethyl methacrylate (HEMA), and 55 g of ethylmethyl ketone, and 0.6 g (0.004 mol) of AIBN was further added, followedby stirring at 75° C. for six hours. The contents after completion ofthe reaction were added dropwise to 500 g of n-heptane, whereby a whiteprecipitate was obtained. After filtration, the residue was dried underreduced pressure at a temperature of 60° C., whereby 19 g of acomparative polymer 5 in the form of a white solid was obtained at ayield of 80%.

<NMR Measurement Results>

The content ratio of the repeating units in the comparative polymer 5 interms of the molar ratio was (MA-C6F-derived repeatingunit):(MAA-derived repeating unit):(HEMA-derived repeatingunit)=14:52:34.

<GPC Measurement Results>

Mw=5,000, Mw/Mn=1.4

3-6. Molar Ratio of Repeating Units and Molecular Weight ofFluorine-Containing Copolymers 1 to 10 and Comparative Polymers 1 to 5

Table 1 shows the repeating units contained and the molar ratiosthereof, the weight average molecular weights (Mw), the molecular weightdispersion (Mw/Mn), and the yields of the obtained fluorine-containingcopolymers 1 to 10 and comparative polymers 1 to 5.

TABLE 1 Composition (repeating units) (mol %) Molecular weight YieldPolymer A B C Mw Mw/Mn (%) Fluorine-containing MA-C6F — BTFBE 7,300 1.437 copolymer 1 28 72 Fluorine-containing MA-C6F 4-HFASt BTFBE 13,300 1.352 copolymer 2 17 37 46 Fluorine-containing MA-C6F p-HO-St BTFBE 17,5001.4 55 copolymer 3 12 38 50 Fluorine-containing HFIP-M p-HO-St BTFBE15,200 1.4 51 copolymer 4 15 39 46 Fluorine-containing MA-CH2-OFCPp-HO-St BTFBE 16,100 1.5 54 copolymer 5 13 38 49 Fluorine-containingV-C6F p-HO-St BTFBE 11,900 1.4 41 copolymer 6 10 38 52Fluorine-containing HFIP-M HEMA — 16,600 1.7 80 copolymer 7 68 32Fluorine-containing HFIP-M HEMA VAc 55,500 2.1 78 copolymer 8 68 25 7Fluorine-containing MA-C6F p-HO-St BTFBE 7,500 1.4 86 copolymer 9 30 5020 Fluorine-containing MA-C6F VBA BTFBE 8,000 1.4 85 copolymer 10 30 5020 Comparative polymer 1 HFIP-M — — 11,200 1.4 70 100 Comparativepolymer 2 MA-C6F — — 13,800 1.6 74 100 Comparative polymer 3 HFIP-M 51 —— 14,700 1.7 80 MA-C6F 49 Comparative polymer 4 Composition disclosed inPatent Literature 4 11,000 1.5 — Comparative polymer 5 MA-C6F HEMA 34 —5,000 1.4 80 14 MAA 52 MA-C6F: 2-(Perfluorohexyl)ethyl methacrylateBTFBE: 1,1-Bis(trifluoromethyl)butadiene 4-HFA-St:1,1,1,3,3,3-Hexafluoro-2-(4-vinylphenyl)propan-2-ol HO-St:p-Hydroxystyrene VBA: p-Vinylbenzoic acid HFIP-M: Hexafluoroisopropylmethacrylate MA-CH2-OFCP: synthesized in example V-C6F:2-(Perfluorohexyl)ethyl vinyl ether HEMA: 2-Hydroxyethyl methacrylateVac: Vinyl acetate MAA: Methacrylic acid “—” in the table means “notcontained”

4. Lyophobicity of Each Polymer Film Before and after UV/Ozone Cleaningor Oxygen Plasma Cleaning and after Heating

A film was formed on a silicon wafer using each of thefluorine-containing copolymers 1 to 10 and comparative polymers 1 to 5.The contact angle with water, anisole, propylene glycol monomethyl etheracetate (PGMEA), or xylene was measured before and after UV/ozonecleaning or oxygen plasma cleaning and after heating. Water, anisole,PGMEA, and xylene are each usable as an ink solvent.

[Production of Silicon Wafer with Film]

Each of the fluorine-containing copolymers 1 to 6, 9, and 10 andcomparative polymers 1 to 5 was dissolved in propylene glycol monomethylether acetate (PGMEA) to a concentration to provide a predetermined filmthickness and applied onto a silicon wafer using a spin coater, therebyforming a coat. Then, the silicon wafer was heated on a hot plate at230° C. for 60 minutes to obtain a silicon wafer with a film.

The fluorine-containing copolymers 7 and 8 contain many OH groups, andcrosslinking of the OH groups leads to exhibition of lyophobicity. Afterpreparation of the following coating liquid, the coating liquid wasapplied onto a silicon wafer using a spin coater to form a coat. Then,the silicon wafer was pre-baked on a hot plate at 100° C. for 150seconds, and the entire surface of the film was subjected to exposureand heated at 230° C. for 60 minutes. The exposure device used was MaskAligner MA 6 produced by SUSS MicroTec KK.

[Preparation of Coating Liquid Containing Fluorine-Containing Copolymer7 or Fluorine-Containing Copolymer 8]

An amount of 1 g of the fluorine-containing copolymer 7 or thefluorine-containing copolymer 8, 0.2 g of2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine as a crosslinkingagent, and 0.01 g of a photoacid generator (2-[2-(4-methylphenylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile)were dissolved in 4 g of PGMEA, and the solution was stirred at roomtemperature for three hours, whereby a coating liquid containing thefluorine-containing copolymer 7 or the fluorine-containing copolymer 8was prepared. The photoacid generator was decomposed by the exposureafter formation of a coat to generate an acid, and crosslinking causedby the acid reduced the OH groups. Thus, lyophobicity was obtained.

[Cleaning Step and Heating Step]

The UV/ozone cleaning device used was PL17-110 produced by Sen LightsCo., Ltd. The oxygen plasma cleaning device used was Plasma dry cleanerPDC210 produced by Yamato Scientific Co., Ltd. Using such a device, eachsilicon wafer with a film was subjected to UV/ozone cleaning or oxygenplasma cleaning for 10 minutes. Then, the silicon wafer was heated at200° C. for 60 seconds.

[Measurement of Contact Angle]

The contact angle of the film surface on the silicon wafer with water,anisole, PGMEA, or xylene was measured before and after UV/ozonecleaning or oxygen plasma cleaning and after the subsequent heatingusing a contact angle meter (DMs-601 produced by Kyowa Interface ScienceCo., Ltd.).

[Measurement of Film Thickness]

The thickness of the film on the silicon wafer was measured using acontact-type film thickness meter before and after UV/ozone cleaning oroxygen plasma cleaning and after the subsequent heating.

[Measurement of Molecular Weight]

The film on the silicon wafer was dissolved in THF and the molecularweight was measured by GPC described above before and after UV/ozonecleaning or oxygen plasma cleaning and after the subsequent heating.

Table 2 shows the contact angle with water or anisole and the filmthickness measured before and after UV/ozone cleaning and after thesubsequent heating.

TABLE 2 Contact angle (°) Water Anisole Film thickness (nm) UV/ozonecleaning After UV/ozone cleaning After UV/ozone cleaning After ExamplePolymer Before After heating Before After heating Before After heatingExample 1 Fluorine-containing 105 92 105 77 45 76 1800 1710 1659copolymer 1 Example 2 Fluorine-containing 101 78 99 58 38 56 1780 17201670 copolymer 2 Example 3 Fluorine-containing 110 61 102 63 35 61 19001700 1650 copolymer 3 Example 4 Fluorine-containing 102 61 100 55 33 541850 1680 1640 copolymer 4 Example 5 Fluorine-containing 98 71 95 54 3752 1950 1800 1770 copolymer 5 Example 6 Fluorine-containing 105 77 10363 39 62 1900 1750 1720 copolymer 6 Example 7 Fluorine-containing 103 65102 63 35 61 1700 1615 1530 copolymer 7 Example 8 Fluorine-containing102 64 101 62 33 59 1750 1680 1590 copolymer 8 Example 9Fluorine-containing 106 55 105 70 34 71 1900 1800 1750 copolymer 9Example 10 Fluorine-containing 104 72 104 68 55 68 1900 1810 1760copolymer 10 Comparative Comparative 105 61 68 61 28 33 1450 360 250Example 1 polymer 1 Comparative Comparative 115 88 98 85 37 45 1900 510450 Example 2 polymer 2 Comparative Comparative 110 72 90 77 31 38 1700450 410 Example 3 polymer 3 Comparative Comparative 101 89 90 55 47 491990 1960 1950 Example 4 polymer 4 Comparative Comparative 101 35 20 5426 31 1990 730 500 Example 5 polymer 5

As shown in Table 2, in the case of the film containing any of thefluorine-containing copolymers 1 to 10 on the silicon wafer, the contactangles with water and anisole were decreased after UV/ozone cleaning butrecovered after heating to almost the same angles as those beforeUV/ozone cleaning. In comparison, the contact angles in the case of anyof the comparative polymers 1 to 5 were only slightly recovered byheating.

Table 3 shows values of D_(W0) obtained by subtracting the contact anglewith water before UV/ozone cleaning from the contact angle with waterafter UV/ozone cleaning, D_(W1) obtained by subtracting the contactangle with water after UV/ozone cleaning from the contact angle withwater after heating, D_(A0) obtained by subtracting the contact anglewith anisole before UV/ozone cleaning from the contact angle withanisole after UV/ozone cleaning, and DA, obtained by subtracting thecontact angle with anisole after UV/ozone cleaning from the contactangle with anisole after heating. Table 3 also shows values ofD_(W1)/D_(W0) and D_(A1)/D_(A0).

TABLE 3 Water Anisole UV/ozone cleaning UV/ozone cleaning ExamplePolymer D_(W0) D_(W1) D_(W1)/D_(W0) D_(A0) D_(A1) D_(A1)/D_(A0) Example1 Fluorine-containing 13 13 1.00 32 31 0.97 copolymer 1 Example 2Fluorine-containing 23 21 0.91 20 18 0.90 copolymer 2 Example 3Fluorine-containing 49 41 0.84 28 26 0.93 copolymer 3 Example 4Fluorine-containing 41 39 0.95 22 21 0.95 copolymer 4 Example 5Fluorine-containing 27 24 0.89 17 15 0.88 copolymer 5 Example 6Fluorine-containing 28 26 0.93 24 23 0.96 copolymer 6 Example 7Fluorine-containing 38 37 0.97 28 26 0.93 copolymer 7 Example 8Fluorine-containing 38 37 0.97 29 26 0.90 copolymer 8 Example 9Fluorine-containing 51 50 0.98 36 37 1.03 copolymer 9 Example 10Fluorine-containing 32 32 1.00 13 13 1.00 copolymer 10 ComparativeExample 1 Comparative polymer 1 44 7 0.16 33 5 0.15 Comparative Example2 Comparative polymer 2 27 10 0.37 48 8 0.17 Comparative Example 3Comparative polymer 3 38 18 0.47 46 7 0.15 Comparative Example 4Comparative polymer 4 12 1 0.08 8 2 0.25 Comparative Example 5Comparative polymer 5 66 −15 −0.23 28 5 0.18

Table 4 shows the contact angle with water or anisole and the filmthickness measured before and after oxygen plasma cleaning and after thesubsequent heating.

TABLE 4 Contact angle (°) Water Anisole Film thickness (nm) Oxygenplasma cleaning After Oxygen plasma cleaning After Oxygen plasmacleaning After Example Polymer Before After heating Before After heatingBefore After heating Example 1 Fluorine-containing 105 89 104 77 45 751800 1680 1580 copolymer 1 Example 2 Fluorine-containing 101 75 99 58 3657 1780 1670 1620 copolymer 2 Example 3 Fluorine-containing 110 55 10363 31 62 1900 1650 1600 copolymer 3 Example 4 Fluorine-containing 102 54101 55 32 55 1850 1600 1590 copolymer 4 Example 5 Fluorine-containing 9865 94 54 35 53 1950 1750 1720 copolymer 5 Example 6 Fluorine-containing105 70 104 63 33 60 1900 1700 1670 copolymer 6 Example 7Fluorine-containing 103 60 101 63 32 58 1700 1550 1480 copolymer 7Example 8 Fluorine-containing 102 59 101 62 35 58 1750 1600 1530copolymer 8 Example 9 Fluorine-containing 106 50 105 70 31 70 1900 17401700 copolymer 9 Example 10 Fluorine-containing 104 68 104 68 50 69 19001790 1710 copolymer 10 Comparative Comparative 105 52 70 61 28 21 1450300 190 Example 1 polymer 1 Comparative Comparative 115 89 92 85 35 261900 410 390 Example 2 polymer 2 Comparative Comparative 110 61 84 77 3127 1700 350 360 Example 3 polymer 3 Comparative Comparative 101 91 87 5546 46 1990 1900 1870 Example 4 polymer 4 Comparative Comparative 101 2915 64 26 18 1990 650 360 Example 5 polymer 5

As shown in Table 4, in the case of the film containing any of thefluorine-containing copolymers 1 to 10 on the silicon wafer, the contactangles with water and anisole were decreased after oxygen plasmacleaning but recovered after heating to almost the same angles as thosebefore oxygen plasma cleaning. In comparison, the contact angles in thecase of any of the comparative polymers 1 to 5 were only slightlyrecovered by heating.

Table 5 shows the values of Do obtained by subtracting the contact anglewith water before oxygen plasma cleaning from the contact angle withwater after oxygen plasma cleaning, D_(W1) obtained by subtracting thecontact angle with water after oxygen plasma cleaning from the contactangle with water after heating, D_(A0) obtained by subtracting thecontact angle with anisole before oxygen plasma cleaning from thecontact angle with anisole after oxygen plasma cleaning, and D_(A1)obtained by subtracting the contact angle with anisole after oxygenplasma cleaning from the contact angle with anisole after heating. Table5 also shows the values of D_(W1)/D_(W0) and D_(A1)/D_(A0).

TABLE 5 Water Anisole Oxygen plasma cleaning Oxygen plasma cleaningExample Polymer D_(W0) D_(W1) D_(W1)/D_(W0) D_(A0) D_(A1) D_(A1)/D_(A0)Example 1 Fluorine-containing 16 15 0.94 32 30 0.94 copolymer 1 Example2 Fluorine-containing 26 24 0.92 22 21 0.95 copolymer 2 Example 3Fluorine-containing 55 48 0.87 32 31 0.97 copolymer 3 Example 4Fluorine-containing 48 47 0.98 23 23 1.00 copolymer 4 Example 5Fluorine-containing 33 29 0.88 19 18 0.95 copolymer 5 Example 6Fluorine-containing 35 34 0.97 30 27 0.90 copolymer 6 Example 7Fluorine-containing 43 41 0.95 31 26 0.84 copolymer 7 Example 8Fluorine-containing 43 42 0.98 27 23 0.85 copolymer 8 Example 9Fluorine-containing 56 55 0.98 39 39 1.00 copolymer 9 Example 10Fluorine-containing 36 36 1.00 18 19 1.06 copolymer 10 ComparativeExample 1 Comparative polymer 1 53 18 0.34 33 −7 −0.21 ComparativeExample 2 Comparative polymer 2 26 3 0.12 50 −9 −0.18 ComparativeExample 3 Comparative polymer 3 49 23 0.47 46 −4 −0.09 ComparativeExample 4 Comparative polymer 4 10 −4 −0.40 9 0 0.00 Comparative Example5 Comparative polymer 5 72 −14 −0.19 28 −8 −0.29

Table 6 shows the contact angle with PGMEA or xylene and the filmthickness measured before and after UV/ozone cleaning and after thesubsequent heating.

TABLE 6 Contact angle (°) PGMEA Xylene Film thickness (nm) UV/ozonecleaning After UV/ozone cleaning After UV/ozone cleaning After ExamplePolymer Before After heating Before After heating Before After heatingExample 1 Fluorine-containing 61 35 61 66 38 65 1800 1710 1659 copolymer1 Example 2 Fluorine-containing 45 26 44 51 33 51 1780 1720 1670copolymer 2 Example 3 Fluorine-containing 48 26 48 53 30 53 1900 17001650 copolymer 3 Example 4 Fluorine-containing 42 25 41 55 34 54 18501680 1640 copolymer 4 Example 5 Fluorine-containing 42 21 42 49 28 481950 1800 1770 copolymer 5 Example 6 Fluorine-containing 49 24 48 53 2453 1900 1750 1720 copolymer 6 Example 7 Fluorine-containing 48 27 45 5227 49 1700 1615 1530 copolymer 7 Example 8 Fluorine-containing 47 25 4451 26 49 1750 1680 1590 copolymer 8 Example 9 Fluorine-containing 53 3054 59 39 60 1900 1800 1750 copolymer 9 Example 10 Fluorine-containing 5222 53 60 22 60 1900 1810 1760 copolymer 10 Comparative Comparative 45 2018 51 21 16 1450 360 250 Example 1 polymer 1 Comparative Comparative 6521 17 69 25 20 1900 510 450 Example 2 polymer 2 Comparative Comparative66 20 15 70 22 14 1700 450 410 Example 3 polymer 3 ComparativeComparative 45 41 40 50 46 43 1990 1960 1950 Example 4 polymer 4Comparative Comparative 42 21 20 54 25 14 1990 730 500 Example 5 polymer5

As shown in Table 6, in the case of the film containing any of thefluorine-containing copolymers 1 to 10 on the silicon wafer, the contactangles with PGMEA and xylene were decreased after UV/ozone cleaning butrecovered after heating to almost the same angles as those beforeUV/ozone cleaning. In comparison, the contact angles in the case of anyof the comparative polymers 1 to 5 were only slightly recovered byheating.

Table 7 shows the values of D_(P0) obtained by subtracting the contactangle with PGMEA before UV/ozone cleaning from the contact angle withPGMEA after UV/ozone cleaning, Dei obtained by subtracting the contactangle with PGMEA after UV/ozone cleaning from the contact angle withwater after heating, D_(X0) obtained by subtracting the contact anglewith xylene before UV/ozone cleaning from the contact angle with xyleneafter UV/ozone cleaning, and D_(X1) obtained by subtracting the contactangle with xylene after UV/ozone cleaning from the contact angle withxylene after heating. Table 7 also shows the values of D_(P1)/D_(P0) andD_(X1)/D_(X0).

TABLE 7 PGMEA Xylene UV/ozone cleaning UV/ozone cleaning Example PolymerD_(P0) D_(P1) D_(P1)/D_(P0) D_(X0) D_(X1) D_(X1)/D_(X0) Example 1Fluorine-containing 26 26 1.00 28 27 0.96 copolymer 1 Example 2Fluorine-containing 19 18 0.95 18 18 1.00 copolymer 2 Example 3Fluorine-containing 22 22 1.00 23 23 1.00 copolymer 3 Example 4Fluorine-containing 17 16 0.94 21 20 0.95 copolymer 4 Example 5Fluorine-containing 21 21 1.00 21 20 0.95 copolymer 5 Example 6Fluorine-containing 25 24 0.96 29 29 1.00 copolymer 6 Example 7Fluorine-containing 21 18 0.86 25 22 0.88 copolymer 7 Example 8Fluorine-containing 22 19 0.86 25 23 0.92 copolymer 8 Example 9Fluorine-containing 23 24 1.04 20 21 1.05 copolymer 9 Example 10Fluorine-containing 30 31 1.03 38 38 1.00 copolymer 10 ComparativeExample 1 Comparative polymer 1 25 −2 −0.08 30 −5 −0.17 ComparativeExample 2 Comparative polymer 2 44 −4 −0.09 44 −5 −0.11 ComparativeExample 3 Comparative polymer 3 46 −5 −0.11 48 −8 −0.17 ComparativeExample 4 Comparative polymer 4 4 −1 −0.25 4 −3 −0.75 ComparativeExample 5 Comparative polymer 5 21 −1 −0.05 29 −11 −0.38

Table 8 shows the contact angle with PGMEA or xylene and the filmthickness measured before and after oxygen plasma cleaning and after thesubsequent heating.

TABLE 8 Contact angle (°) PGMEA Xylene Film thickness (nm) Oxygen plasmacleaning After Oxygen plasma cleaning After Oxygen plasma cleaning AfterExample Polymer Before After heating Before After heating Before Afterheating Example 1 Fluorine-containing 61 32 61 66 34 65 1800 1680 1580copolymer 1 Example 2 Fluorine-containing 45 21 45 51 28 50 1780 16701620 copolymer 2 Example 3 Fluorine-containing 48 22 47 53 27 52 19001650 1600 copolymer 3 Example 4 Fluorine-containing 42 20 40 55 30 551850 1600 1590 copolymer 4 Example 5 Fluorine-containing 42 19 41 49 2448 1950 1750 1720 copolymer 5 Example 6 Fluorine-containing 49 20 47 5321 52 1900 1700 1670 copolymer 6 Example 7 Fluorine-containing 48 23 4452 24 47 1700 1550 1480 copolymer 7 Example 8 Fluorine-containing 47 2243 51 22 46 1750 1600 1530 copolymer 8 Example 9 Fluorine-containing 5328 53 59 34 59 1900 1740 1700 copolymer 9 Example 10 Fluorine-containing52 22 52 60 21 61 1900 1790 1710 copolymer 10 Comparative Comparative 4515 10 51 18 20 1450 300 190 Example 1 polymer 1 Comparative Comparative65 12 11 69 15 21 1900 410 390 Example 2 polymer 2 ComparativeComparative 66 15 13 70 12 17 1700 350 360 Example 3 polymer 3Comparative Comparative 45 37 36 50 41 39 1990 1900 1870 Example 4polymer 4 Comparative Comparative 42 14 14 54 19 13 1990 650 360 Example5 polymer 5

As shown in Table 8, in the case of the film containing any of thefluorine-containing copolymers 1 to 10 on the silicon wafer, the contactangles with PGMEA and xylene were decreased after oxygen plasma cleaningbut recovered after heating to almost the same angles as those beforeoxygen plasma cleaning. In comparison, the contact angles in the case ofany of the comparative polymers 1 to 5 were only slightly recovered byheating.

Table 9 shows the values of D_(P0) obtained by subtracting the contactangle with PGMEA before oxygen plasma cleaning from the contact anglewith PGMEA after oxygen plasma cleaning, D_(P1) obtained by subtractingthe contact angle with PGMEA after oxygen plasma cleaning from thecontact angle with water after heating, D_(X0) obtained by subtractingthe contact angle with xylene before oxygen plasma cleaning from thecontact angle with xylene after oxygen plasma cleaning, and D_(X1)obtained by subtracting the contact angle with xylene after oxygenplasma cleaning from the contact angle with xylene after heating. Table9 also shows the values of D_(P1)/D_(P0) and D_(X1)/D_(X0).

TABLE 9 PGMEA Xylene Oxygen plasma cleaning Oxygen plasma cleaningExample Polymer D_(P0) D_(P1) D_(P1)/D_(P0) D_(X0) D_(X1) D_(X1)/D_(X0)Example 1 Fluorine-containing 29 29 1.00 32 31 0.97 copolymer 1 Example2 Fluorine-containing 24 24 1.00 23 22 0.96 copolymer 2 Example 3Fluorine-containing 26 25 0.96 26 25 0.96 copolymer 3 Example 4Fluorine-containing 22 20 0.91 25 25 1.00 copolymer 4 Example 5Fluorine-containing 23 22 0.96 25 24 0.96 copolymer 5 Example 6Fluorine-containing 29 27 0.93 32 31 0.97 copolymer 6 Example 7Fluorine-containing 25 21 0.84 28 23 0.82 copolymer 7 Example 8Fluorine-containing 25 21 0.84 29 24 0.83 copolymer 8 Example 9Fluorine-containing 25 25 1.00 25 25 1.00 copolymer 9 Example 10Fluorine-containing 30 30 1.00 39 40 1.03 copolymer 10 ComparativeExample 1 Comparative polymer 1 30 −5 −0.17 33 2 0.06 ComparativeExample 2 Comparative polymer 2 53 −1 −0.02 54 6 0.11 ComparativeExample 3 Comparative polymer 3 51 −2 −0.04 51 −2 −0.04 ComparativeExample 4 Comparative polymer 4 8 −1 −0.13 9 −2 −0.22 ComparativeExample 5 Comparative polymer 5 28 0 0.00 35 −6 −0.17

Table 10 shows the results of the measurement by GPC described aboveperformed on the film on the silicon wafer dissolved in THF before andafter UV/ozone cleaning or oxygen plasma cleaning and after thesubsequent heating.

TABLE 10 Molecular weight (Mw) UV/ozone cleaning After Oxygen plasmacleaning After Example Polymer Before After heating Before After heatingExample 1 Fluorine-containing 7,300 6,900 6,800 7,300 6,900 6,800copolymer 1 Example 2 Fluorine-containing 13,300 12,800 13,300 13,30013,300 13,300 copolymer 2 Example 3 Fluorine-containing 17,500 16,90016,700 17,500 16,400 16,000 copolymer 3 Example 4 Fluorine-containing15,200 14,800 14,500 15,200 14,600 14,200 copolymer 4 Example 5Fluorine-containing 16,100 15,900 15,400 16,100 15,500 15,000 copolymer5 Example 6 Fluorine-containing 11,900 11,000 10,900 11,900 10,80010,500 copolymer 6 Example 7 Fluorine-containing 16,600 12,000 10,00016,600 11,000 9,000 copolymer 7 Example 8 Fluorine-containing 55,50048,000 43,000 55,500 45,000 42,000 copolymer 8 Example 9Fluorine-containing 7,500 7,400 7,350 7,500 7,400 7,300 copolymer 9Example 10 Fluorine-containing 8,000 7,800 7,800 8,000 7,800 7,800copolymer 10 Comparative Example 1 Comparative polymer 1 11,200 800 50011,200 430 380 Comparative Example 2 Comparative polymer 2 13,800 1,100610 13,800 510 450 Comparative Example 3 Comparative polymer 3 14,7001,300 450 14,700 810 600 Comparative Example 4 Comparative polymer 411,000 9,000 8,800 11,000 8,000 7,800 Comparative Example 5 Comparativepolymer 5 5,000 1,200 800 5,000 450 450

As shown in Table 10, the molecular weight measured by dissolving thefilm containing any of the fluorine-containing copolymers 1 to 10 on thesilicon wafer in THF was not remarkably changed after UV/ozone cleaningor oxygen plasma cleaning, which shows that decomposition of the polymerwas suppressed. In comparison, the molecular weight in the case of anyof the comparative polymers 1 to 5 was confirmed to be remarkablyreduced.

5. Evaluation as Resist

Resists 2, 3, 7, and 8 and a comparative resist 4 were prepared usingthe fluorine-containing copolymers 2, 3, 7, and 8 and the comparativepolymer 4. The resist performances of these resists were evaluated andcompared.

5-1. Preparation of Resist [Resist 2]

To 1.6 g of the fluorine-containing copolymer 2 were added 20 g (solidcontent of 40% by mass) of BMR C-1000 (product name) that is a negativeresist produced by Tokyo Ohka Kougyo Co., Ltd. and 0.2 g of TPA-100(product name) that is an isocyanate-type crosslinking agent produced byAsahi Kasei Corporation. Thus, a resist 2 was prepared.

[Resist 3]

To 1.6 g of the fluorine-containing copolymer 3 were added 20 g (solidcontent of 40% by mass) of BMR C-1000 (product name) that is a negativeresist produced by Tokyo Ohka Kougyo Co., Ltd., 0.2 g of2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine as a crosslinkingagent, and 0.01 g of a photoacid generator (2-[2-(4-methylphenylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile).Thus, a resist 3 was prepared.

[Resist 7 and 8]

An amount of 1 g of the fluorine-containing copolymer 7 or thefluorine-containing copolymer 8, 0.2 g of2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine as a crosslinkingagent, and 0.01 g of a photoacid generator (2-[2-(4-methylphenylsulfonyloxyimino)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile)were dissolved in 4 g of PGMEA, and the solution was stirred at roomtemperature for three hours. Thus, a resist 7 containing thefluorine-containing copolymer 7 or a resist 8 containing thefluorine-containing copolymer 8 was prepared.

[Comparative Resist 4]

The positive photosensitive resin composition disclosed in PatentLiterature 4 was prepared using the comparative polymer 4. Thus, acomparative resist 4 was obtained.

5-2. Formation of Resist Film

To a silicon wafer (4 inches in diameter) were sprayed super pure waterand then acetone. After cleaning by spin coating, the silicon wafer wassubjected to UV/ozone cleaning using the UV/ozone cleaning devicedescribed above for five minutes. Subsequently, the resists 2, 3, 7, and8 and comparative resist 4 were each filtered through a 0.2-μm membranefilter, and applied onto the silicon wafer using a spinner at a rotationspeed of 1,000 rpm, followed by drying by heating on a hot plate at 100°C. for 150 seconds. Thus, a resist film having a thickness of 2 μm wasformed on the silicon wafer.

5-3. Evaluation of Solubility of Resist in Developing Solution andResolution of Resist Pattern

Evaluation of the solubility of the resist in a developing solution andthe resolution of the resist pattern and measurement of the contactangle were performed on each resist film on the silicon wafer. Themethods for the measurement are described below.

The resist film formed on the silicon wafer was irradiated with i-line(wavelength of 365 nm) using the mask aligner described above through amask (line and space of 5 μm). Thus, exposure was carried out. Then, theresist film was subjected to post-exposure bake at 120° C. for 60seconds.

[Solubility in Developing Solution]

The silicon wafer with a resist film was immersed in an alkalideveloping solution or PGMEA at room temperature for 60 seconds beforeand after the exposure, and the solubility of the resist film in adeveloping solution or an organic solvent was evaluated. The alkalideveloping solution used was a 2.38% by mass aqueous solution oftetramethyl ammonium hydroxide (hereafter, also referred to as TMAH).The solubility of the resist film was evaluated by measuring thethickness of the resist film after immersion with an opticalinterference-type thickness meter. The case where the resist film wascompletely dissolved was evaluated as “Soluble” and the case where theresist film was not dissolved to remain was evaluated as “Insoluble”.

[Sensitivity]

The optimum exposure dose Eop (mj/cm²) upon formation of the patternhaving the line and space mentioned above was obtained and determined asan index of the sensitivity.

[Resolution]

The resist pattern on the silicon wafer with a patterned film wasexamined under a microscope. The resist pattern with no line edgeroughness observed was evaluated as “Excellent”, the resist pattern withslight line edge roughness observed was evaluated as “Good”, and theresist pattern with remarkable line edge roughness observed wasevaluated as “Poor”.

Table 11 shows the evaluation results on the solubility of each resistin a developing solution, and the sensitivity and resolution of theresist pattern.

TABLE 11 Development Resist performance Solubility in alkali solutionSolubility in PGMEA Sensitivity Resist Polymer Unexposed part Afterexposure Unexposed part After exposure (mJ/cm²) Resolution Resist 2Fluorinie-containing Soluble Insoluble Soluble Insoluble 230 Good(negative) copolymer 2 Resist 3 Fluorinie-containing Soluble InsolubleSoluble Insoluble 120 Good (negative) copolymer 3 Resist 7Fluorine-containing Insoluble Insoluble Soluble Insoluble 105 Excellent(negative) copolymer 7 Resist 8 Fluorine-containing Insoluble InsolubleSoluble Insoluble 105 Excellent (negative) copolymer 8 ComparativeComparative Insoluble Soluble Insoluble Insoluble 120 Good resist 4polymer 4 (positive) PGMEA: Propylene glycol monomethyl ether acetate

<Evaluation on Solubility in Developing Solution>

As shown in Table 11, in the case of the resists 2 and 3, an unexposedpart was soluble and an exposed part was insoluble in an alkali solutionand PGMEA. In the case of the resists 7 and 8, an unexposed part wassoluble and an exposed part was insoluble in PGMEA. These resists areusable as negative resists. In the case of the comparative resist 4, anexposed part is soluble in an alkali solution. The comparative resist 4is therefore usable as a positive resist.

<Sensitivity>

The resist 3 and the comparative resist 4 exhibited the similarsensitivity. In comparison with these resists, the resists 7 and 8exhibited higher sensitivity.

<Resolution>

The resist patterns formed using the resists 2, 3, 7, and 8 andcomparative resist 4 each had a line and space of 5 μm transferred fromthe mask at a high resolution. In particular, in the cases of theresists 7 and 8, no line edge roughness was observed, and the resolutionof the resist pattern was evaluated as “Excellent”.

5-4. Evaluation on Lyophobicity Before and after UV/Ozone Cleaning andafter Heating of Resist Pattern

Measurement of the contact angle with anisole was performed on each ofthe resist films on the silicon wafers prepared using the resists 2, 3,7, and 8 and comparative resist 4 before and after UV/ozone cleaning andafter the subsequent heating. The silicon wafer with a resist film wassubjected to UV/ozone cleaning using the UV/ozone cleaning devicedescribed above for 10 minutes and then heated at 200° C. for 60seconds. The contact angle meter used was produced by Kyowa InterfaceScience Co., Ltd.

TABLE 12 Contact angle (°) Unexposed part Exposed part UV/ozone cleaningAfter UV/ozone cleaning After Resist Polymer Before After heating BeforeAfter heating Resist 2 Fluorinie-containing 45 10 10 62 38 58 (negative)copolymer 2 Resist 3 Fluorinie-containing 47 10 10 65 37 63 (negative)copolymer 3 Resist 7 Fluorine-containing 42 10 10 63 35 61 (negative)copolymer 7 Resist 8 Fluorine-containing 59 10 10 62 32 60 (negative)copolymer 8 Comparative Comparative 55 48 50 42 10 10 resist 4 polymer 4(positive)

[Measurement Results of Contact Angle]

As shown in Table 12, in the case of the resists 2, 3, 7, and 8, thecontact angle of an exposed part that served as a bank in the patternwith anisole was decreased by UV/ozone cleaning but increased by heatingto recover the lyophobicity.

5-5. Evaluation on Lyophobicity Before and after Oxygen Plasma Cleaningand after Heating of Resist Pattern

Measurement of the contact angle with anisole was performed on each ofthe resist films on the silicon wafers prepared using the resists 2, 3,7, and 8 and comparative resist 4 before and after oxygen plasmacleaning and after the subsequent heating. The silicon wafer with aresist film was subjected to oxygen plasma cleaning using the oxygenplasma cleaning device described above for 10 minutes and then heated at200° C. for 60 seconds. The contact angle meter used was produced byKyowa Interface Science Co., Ltd.

TABLE 13 Contact angle (°) Unexposed part Exposed part Oxygen plasmacleaning After Oxygen plasma cleaning After Resist Polymer Before Afterheating Before After heating Resist 2 Fluorinie-containing 45 10 10 6239 61 (negative) copolymer 2 Resist 3 Fluorinie-containing 47 10 10 6536 65 (negative) copolymer 3 Resist 7 Fluorine-containing 42 10 10 63 3356 (negative) copolymer 7 Resist 8 Fluorine-containing 59 10 10 62 30 57(negative) copolymer 8 Comparative Comparative 55 45 45 42 10 10 resist4 polymer 4 (positive)

[Measurement Results of Contact Angle]

As shown in Table 13, in the case of the resists 2, 3, 7, and 8, thecontact angle of an exposed part that served as a bank in the patternwith anisole was decreased by oxygen plasma cleaning but increased byheating to recover the lyophobicity.

INDUSTRIAL APPLICABILITY

The production method of a substrate with a patterned film of thepresent disclosure can allow a bank to have sufficient lyophobicitywhile maintaining the lyophilicity of a recess of a patterned film. Theproduction method of a substrate with a patterned film of the presentdisclosure therefore can be used not only for production of a displayelement by an ink-jet method but also for production of an organicsemiconductor film or a thin film of a colored resin or the like andproduction of display wiring and a devices such as a thin filmtransistor.

1. A method for producing a substrate with a patterned film, the methodcomprising: a cleaning step of performing UV/ozone cleaning or oxygenplasma cleaning on a substrate with a patterned film comprising asubstrate and a patterned film on the substrate, to obtain a firstsubstrate with a patterned film; and a heating step of heating the firstsubstrate with a patterned film to obtain a second substrate with apatterned film, wherein the patterned film of the first substrate with apatterned film has a contact angle decreased in the cleaning step, andthe patterned film of the second substrate with a patterned film has acontact angle recovered in the heating step.
 2. The production methodaccording to claim 1, wherein an angle obtained by subtracting a contactangle with anisole of the patterned film of the first substrate with apatterned film from a contact angle with anisole of the patterned filmof the second substrate with a patterned film is represented by D_(A1),and D_(A1) is 10° or larger.
 3. The production method according to claim2, wherein an angle obtained by subtracting the contact angle withanisole of the patterned film of the first substrate with a patternedfilm from a contact angle with anisole of the patterned film before thecleaning step is represented by D_(A0), and a value of D_(A1)/D_(A0) is0.30 or larger.
 4. The production method according to claim 1, whereinan angle obtained by subtracting a contact angle with water of thepatterned film of the first substrate with a patterned film from acontact angle with water of the patterned film of the second substratewith a patterned film is represented by D_(W1), D_(W1) is 10° or larger,an angle obtained by subtracting the contact angle with water of thepatterned film of the first substrate with a patterned film from acontact angle with water of the patterned film before the cleaning stepis represented by D_(W0), and a value of D_(W1)/D_(W0) is 0.50 orlarger.
 5. The production method according to claim 1, wherein an angleobtained by subtracting a contact angle with propylene glycol monomethylether acetate of the patterned film of the first substrate with apatterned film from a contact angle with propylene glycol monomethylether acetate of the patterned film of the second substrate with apatterned film is represented by D_(P1), and D_(P1) is 10° or larger. 6.The production method according to claim 5, wherein an angle obtained bysubtracting the contact angle with propylene glycol monomethyl etheracetate of the patterned film of the first substrate with a patternedfilm from a contact angle with propylene glycol monomethyl ether acetateof the patterned film before the cleaning step is represented by D_(P0),and a value of D_(P1)/D_(P0) is 0.30 or larger.
 7. The production methodaccording to claim 1, wherein an angle obtained by subtracting a contactangle with xylene of the patterned film of the first substrate with apatterned film from a contact angle with xylene of the patterned film ofthe second substrate with a patterned film is represented by D_(X1), andD_(X1) is 15° or larger.
 8. The production method according to claim 7,wherein an angle obtained by subtracting the contact angle with xyleneof the patterned film of the first substrate with a patterned film froma contact angle with xylene of the patterned film before the cleaningstep is represented by D_(X0), and a value of D_(X1)/D_(X0) is 0.80 orlarger.
 9. The production method according to claim 1, wherein thepatterned film of the first substrate with a patterned film has acontact angle with water of 50° or larger and a contact angle withanisole of 30 or larger, and the patterned film of the second substratewith a patterned film has a contact angle with water of 93° or largerand a contact angle with anisole of 50° or larger.
 10. The productionmethod according to claim 1, wherein the patterned film of the firstsubstrate with a patterned film has a contact angle with propyleneglycol monomethyl ether acetate of 190 or larger and a contact anglewith xylene of 200 or larger, and the patterned film of the secondsubstrate with a patterned film has a contact angle with propyleneglycol monomethyl ether acetate of 40 or larger and a contact angle withxylene of 450 or larger.
 11. The production method according to claim 1,wherein the patterned film contains a fluorine-containing copolymerhaving a repeating unit represented by the following formula (A):

wherein R¹ is a hydrogen atom, a fluorine atom, or a C1-C20 alkyl groupin which hydrogen atoms bonded to a carbon atom are optionally partly orentirely replaced by fluorine atoms; Q is a C1-C20 fluoroalkyl groupoptionally containing a hydrogen atom, an oxygen atom, or a nitrogenatom; X is a single bond or a divalent group; and O is an oxygen atom.12. The production method according to claim 11, wherein thefluorine-containing copolymer is any one of the followingfluorine-containing copolymers (1) to (3): the fluorine-containingcopolymer (1) containing both the repeating unit represented by thefollowing formula (A) and a repeating unit represented by the followingformula (B):

wherein R¹ and R² are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X and Y are each independently a singlebond or a divalent group, O is an oxygen atom; and H is a hydrogen atom;the fluorine-containing copolymer (2) containing both the repeating unitrepresented by the following formula (A) and a repeating unitrepresented by the following formula (C):

wherein R¹ and R³ are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X is a single bond or a divalent group;Z is a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynylgroup, a C6-C20 phenyl group, a C1-C20 alkoxy group, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and a hydrogen atom in any of theforegoing groups is optionally replaced by a fluorine atom, an oxygenatom, or a nitrogen atom; and O is an oxygen atom; Thefluorine-containing copolymer (3) containing all of the repeating unitrepresented by the following formula (A), the repeating unit representedby the following formula (B), and the repeating unit represented by thefollowing formula (C):

wherein R¹, R², R³ are each independently a hydrogen atom, a fluorineatom, or a C1-C20 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; Q isa C1-C20 fluoroalkyl group optionally containing a hydrogen atom, anoxygen atom, or a nitrogen atom; X and Y are each independently a singlebond or a divalent group; Z is a C1-C20 alkyl group, a C2-C20 alkenylgroup, a C2-C20 alkynyl group, a C6-C20 phenyl group, a C1-C20 alkoxygroup, or a C1-C20 alkylcarbonyloxy group or carboxyl group, and ahydrogen atom in any of the foregoing groups is optionally replaced by afluorine atom, an oxygen atom, or a nitrogen atom; O is an oxygen atom;and H is a hydrogen atom.
 13. The production method according to claim1, wherein the first substrate with a patterned film is heated at atemperature of 50° C. or higher but 350° C. or lower for 10 seconds orlonger in the heating step.
 14. The production method according to claim1, wherein the second substrate with a patterned film is a substrate forforming a display element by an ink-jet method.
 15. The productionmethod according to claim 11, wherein Q is a C3-C10 fluoroalkyl groupand X is a carbonyl group in the repeating unit represented by theformula (A).
 16. The production method according to claim 15, wherein Qis a perfluorohexyl ethyl group and X is a carbonyl group in therepeating unit represented by the formula (A).
 17. The production methodaccording to claim 15, wherein Q is a hexafluoroisopropyl group and X isa carbonyl group in the repeating unit represented by the formula (A).18. The production method according to claim 11, wherein the repeatingunit represented by the formula (A) is a repeating unit represented bythe following formula (4):

wherein R⁴ and R⁵ are each independently a hydrogen atom, a fluorineatom, or a C1-C3 alkyl group in which hydrogen atoms bonded to a carbonatom are optionally partly or entirely replaced by fluorine atoms; O isan oxygen atom; H is a hydrogen atom; and F is a fluorine atom.
 19. Theproduction method according to claim 12, wherein Q is ahexafluoroisopropyl group and X is a carbonyl group in the repeatingunit represented by the formula (A), and Y is a p-phenylene group or acarboxy ethylene group in the repeating unit represented by the formula(B).
 20. The production method according to claim 12, wherein Q is ahexafluoroisopropyl group and X is a carbonyl group in the repeatingunit represented by the formula (A); Y is a p-phenylene group or acarboxy ethylene group in the repeating unit represented by the formula(B); and Z is an alkoxy group, a carboxyl group, an acetoxy group, or abis(trifluoromethyl)vinyl group in the repeating unit represented by theformula (C).
 21. The production method according to claim 12, wherein Zis a bis(trifluoromethyl)vinyl group in the repeating unit representedby the formula (C).
 22. The production method according to claim 12,wherein Q is a C3-C10 fluoroalkyl group and X is a carbonyl group in therepeating unit represented by the formula (A); Y is a p-phenylene group,a p-phenylene carbonyl group, or a p-phenylene hexafluoroisopropylenegroup in the repeating unit represented by the formula (B); and Z is abis(trifluoromethyl)vinyl group in the repeating unit represented by theformula (C).